Catalyst and process for producing a polymer containing a high molecular weight tail

ABSTRACT

The present invention provides metal-containing sulfated activator-supports, and polymerization catalyst compositions employing these activator-supports. Methods for making these metal-containing sulfated activator-supports and for using such components in catalyst compositions for the polymerization of olefins are also provided.

REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 13/647,411, filed on Oct. 9, 2012, now U.S. Pat. No. 8,637,420,which is a continuation application of U.S. patent application Ser. No.12/400,013, filed on Mar. 9, 2009, now U.S. Pat. No. 8,309,485, thedisclosures of which are incorporated herein by reference in theirentirety.

BACKGROUND OF THE INVENTION

The present invention relates generally to the field of olefinpolymerization catalysis, supported catalyst compositions, methods forthe polymerization and copolymerization of olefins, and polyolefins.More specifically, this invention relates to metal-containing sulfatedactivator-supports, methods for producing such activator-supports, andto catalyst compositions employing these activator-supports.

Polyolefin homopolymers, copolymers, terpolymers, etc., can be producedusing various combinations of catalyst systems and polymerizationprocesses. One method that can be used to produce such polyolefinsemploys a metallocene-based catalyst system. Generally, metallocenecatalysts produce polyolefins with a narrow molecular weightdistribution, and without a high molecular weight tail to the molecularweight distribution. While a polymer having a narrow molecular weightdistribution can be advantageous in certain polymer processingoperations and end-use applications, it can be a drawback in others.Stability in certain polymer processing operations, such as in blownfilm, blow molding, and pipe extrusion, often is reduced with a narrowmolecular weight distribution polymer, as compared to broader molecularweight distribution polymers, resulting in reduced output or productionrates. The high molecular weight tail, or fraction, of the molecularweight distribution can provide higher melt strength and/or higher zeroshear viscosity to the polymer which can improve processability andcertain end-use properties in blown film, blow molding, pipe extrusion,and other related applications.

Hence, it would be beneficial to produce a relatively narrow molecularweight distribution polymer—as compared to, for instance, a polymerproduced using a chromium catalyst—using a metallocene-based catalystsystem, where the polymer has a high molecular weight tail to improveprocessing and end-use properties in certain polyolefin end-useapplications. Accordingly, it is to these ends that the presentinvention is directed.

SUMMARY OF THE INVENTION

The present invention generally relates to metal-containingactivator-supports, catalyst compositions employing these supports,methods for preparing the activator-supports and catalyst compositions,methods for using the catalyst compositions to polymerize olefins, thepolymer resins produced using such catalyst compositions, and articlesproduced using these polymer resins. In accordance with one aspect ofthe present invention, a metal-containing sulfated activator-support isdisclosed which comprises a contact product of:

(i) a transition metal compound;

(ii) a sulfate compound; and

(iii) a solid oxide.

The metal-containing sulfated activator-support can be produced usingdifferent methods of synthesis. One such method to produce ametal-containing sulfated activator-support comprises these steps:

(a) contacting a solid oxide with a sulfate compound to produce asulfated solid oxide;

(b) calcining the sulfated solid oxide to produce a calcined sulfatedsolid oxide; and

(c) contacting the calcined sulfated solid oxide with

-   -   (i) a transition metal compound and a hydrocarbon solvent; or    -   (ii) a vapor comprising a transition metal compound;        to produce the metal-containing sulfated activator-support.

Alternatively, the metal-containing sulfated activator-support can beproduced in accordance with the following procedure:

(a) contacting a solid oxide with a sulfate compound while calcining toproduce a calcined sulfated solid oxide; and

(b) contacting the calcined sulfated solid oxide with

-   -   (i) a transition metal compound and a hydrocarbon solvent; or    -   (ii) a vapor comprising a transition metal compound;        to produce the metal-containing sulfated activator-support.

In either process, an optional step of removing the hydrocarbon solventfrom the metal-containing sulfated activator-support can be employed.Additionally, the solid oxide can be calcined prior to step (a), ifdesired. Once the metal-containing sulfated activator-support has beenproduced, it does not need to be calcined, and generally is notcalcined, prior to use in a catalyst composition for the polymerizationof olefins.

Catalyst compositions containing these metal-containing sulfatedactivator-supports are also provided by the present invention. In oneaspect, the catalyst composition can comprise a contact product of ametallocene compound and a metal-containing sulfated activator-support.The metal-containing sulfated activator-support comprises a contactproduct of (i) a transition metal compound; (ii) a sulfate compound; and(iii) a solid oxide. This catalyst composition can further comprise anorganoaluminum compound. In other aspects, the catalyst compositioncomprising a metallocene compound and a metal-containing sulfatedactivator-support can further comprise an optional co-catalyst. Suitableoptional co-catalysts in this aspect include, but are not limited to,aluminoxane compounds, organozinc compounds, organoboron or organoboratecompounds, ionizing ionic compounds, and the like, or combinationsthereof.

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like. Onesuch process for polymerizing olefins in the presence of a catalystcomposition of the present invention comprises contacting the catalystcomposition with an olefin monomer and optionally an olefin comonomerunder polymerization conditions to produce an olefin polymer, whereinthe catalyst composition comprises a contact product of a metallocenecompound and a metal-containing sulfated activator-support. Theactivator-support comprises a contact product of (i) a transition metalcompound; (ii) a sulfate compound; and (iii) a solid oxide. Otherco-catalysts, including organoaluminum compounds, can be employed inthis process.

Polymers produced from the polymerization of olefins, resulting inhomopolymers or copolymers, for example, can be used to produce variousarticles of manufacture.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a plot of the molecular weight distributions of thepolymers of Examples 1-2.

FIG. 2 presents a plot of the molecular weight distributions of thepolymers of Examples 3-4.

FIG. 3 presents a plot of the molecular weight distributions of thepolymers of Examples 9-10.

FIG. 4 presents a plot of the molecular weight distributions of thepolymers of Examples 11-12.

DEFINITIONS AND ABBREVIATIONS

To define more clearly the terms used herein, the following definitionsand abbreviations are provided. To the extent that any definition orusage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

-   -   Bu—Butyl.    -   CZA-Ti—Titanium-containing chlorided zinc aluminate.    -   CZA-Zr—Zirconium-containing chlorided zinc aluminate.    -   FSA-Ti—Titanium-containing fluorided silica-alumina    -   FSA-Zr—Zirconium-containing fluorided silica-alumina    -   i-Pr—Isopropyl.    -   M—Molecular weight.    -   Me—Methyl.    -   Mn—Number-average molecular weight.    -   Mw—Weight-average molecular weight.    -   Mw/Mn—Ratio is a measure of the molecular weight distribution;        also referred to as the polydispersity index.    -   Mz—Z-average molecular weight.    -   Mz/Mw—Ratio is a measure of the breadth of the high molecular        weight fraction of the polymer.    -   Ph—Phenyl.    -   SA—Sulfated alumina    -   SA-Ti—Titanium-containing sulfated alumina    -   SA-V—Vanadium-containing sulfated alumina    -   SA-Zr—Zirconium-containing sulfated alumina    -   t-Bu—Tert-butyl or t-butyl.    -   TIBA—Triisobutylaluminum.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer isderived from an olefin monomer and one olefin comonomer, while aterpolymer is derived from an olefin monomer and two olefin comonomers.Accordingly, “polymer” encompasses copolymers, terpolymers, etc.,derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene copolymers,ethylene terpolymers, and the like. As an example, an olefin copolymer,such as an ethylene copolymer, can be derived from ethylene and acomonomer, such as 1-butene, 1-hexene, or 1-octene. If the monomer andcomonomer were ethylene and 1-hexene, respectively, the resultingpolymer would be categorized an as ethylene/1-hexene copolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process would involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene), to produce acopolymer.

The term “co-catalyst” is used generally herein to refer toorganoaluminum compounds that can constitute one component of a catalystcomposition. Additionally, “co-catalyst” also refers to other optionalcomponents of a catalyst composition including, but not limited to,aluminoxanes, organoboron or organoborate compounds, and ionizing ioniccompounds, as disclosed herein. The term “co-catalyst” is usedregardless of the actual function of the compound or any chemicalmechanism by which the compound may operate. In one aspect of thisinvention, the term “co-catalyst” is used to distinguish that componentof the catalyst composition from the metallocene component.

The term “fluoroorgano boron compound” is used herein with its ordinarymeaning to refer to neutral compounds of the form BY₃. The term“fluoroorgano borate compound” also has its usual meaning to refer tothe monoanionic salts of a fluoroorgano boron compound of the form[cation]⁺[BY₄]⁻, where Y represents a fluorinated organic group.Materials of these types are generally and collectively referred to as“organoboron or organoborate compounds.”

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions described herein. Combining additional materials orcomponents can be done by any suitable method. Further, the term“contact product” includes mixtures, blends, solutions, slurries,reaction products, and the like, or combinations thereof. Although“contact product” can include reaction products, it is not required forthe respective components to react with one another.

The term “precontacted” mixture is used herein to describe a firstmixture of catalyst components that are contacted for a first period oftime prior to the first mixture being used to form a “postcontacted” orsecond mixture of catalyst components that are contacted for a secondperiod of time. Often, the precontacted mixture describes a mixture ofmetallocene compound (or compounds), olefin monomer, and organoaluminumcompound (or compounds), before this mixture is contacted with anactivator(s) and/or activator-support(s) and optional additionalorganoaluminum compound(s). Thus, precontacted describes components thatare used to contact each other, but prior to contacting the componentsin the second, postcontacted mixture. Accordingly, this invention mayoccasionally distinguish between a component used to prepare theprecontacted mixture and that component after the mixture has beenprepared. For example, according to this description, it is possible forthe precontacted organoaluminum compound, once it is contacted with themetallocene and the olefin monomer, to have reacted to form at least onechemical compound, formulation, or structure different from the distinctorganoaluminum compound used to prepare the precontacted mixture. Inthis case, the precontacted organoaluminum compound or component isdescribed as comprising an organoaluminum compound that was used toprepare the precontacted mixture.

Alternatively, the precontacted mixture can describe a mixture ofmetallocene compound(s) and organoaluminum compound(s), prior tocontacting of this mixture with the activator(s) and/oractivator-support(s). This precontacted mixture also can describe amixture of metallocene compound(s), olefin monomer, and activator(s)and/or activator-support(s), before this mixture is contacted with anorganoaluminum co-catalyst compound or compounds.

Similarly, the term “postcontacted” mixture is used herein to describe asecond mixture of catalyst components that are contacted for a secondperiod of time, and one constituent of which is the “precontacted” orfirst mixture of catalyst components that were contacted for a firstperiod of time. Typically, the term “postcontacted” mixture is usedherein to describe the mixture of metallocene compound(s), olefinmonomer, organoaluminum compound(s), and activator(s) and/oractivator-support(s) formed from contacting the precontacted mixture ofa portion of these components with any additional components added tomake up the postcontacted mixture. For instance, the additionalcomponent added to make up the postcontacted mixture can be anactivator-support, and optionally, can include an organoaluminumcompound which is the same as or different from the organoaluminumcompound used to prepare the precontacted mixture, as described herein.Accordingly, this invention may also occasionally distinguish between acomponent used to prepare the postcontacted mixture and that componentafter the mixture has been prepared.

The term “metallocene,” as used herein, describes a compound comprisingat least one η³ to η⁵-cycloalkadienyl-type moiety, wherein η³ toη⁵-cycloalkadienyl moieties include cyclopentadienyl ligands, indenylligands, fluorenyl ligands, and the like, including partially saturatedor substituted derivatives or analogs of any of these. Possiblesubstituents on these ligands include hydrogen, therefore thedescription “substituted derivatives thereof” in this inventioncomprises partially saturated ligands such as tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl,partially saturated fluorenyl, substituted partially saturated indenyl,substituted partially saturated fluorenyl, and the like. In somecontexts, the metallocene is referred to simply as the “catalyst,” inmuch the same way the term “co-catalyst” is used herein to refer to, forexample, an organoaluminum compound or an aluminoxane compound.Metallocene is also used herein to encompass mono-cyclopentadienyl orhalf-sandwich compounds, as well as compounds containing at least onecyclodienyl ring and compounds containing boratabenzene ligands.Further, metallocene is also used herein to encompass dinuclearmetallocene compounds, i.e., compounds comprising two metallocenemoieties linked by a connecting group, such as an alkenyl groupresulting from an olefin metathesis reaction or a saturated versionresulting from hydrogenation or derivatization.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product resulting from thecontact or reaction of the components of the mixtures, the nature of theactive catalytic site, or the fate of the co-catalyst, the metallocenecompound, any olefin monomer used to prepare a precontacted mixture, orthe activator-support, after combining these components. Therefore, theterms “catalyst composition,” “catalyst mixture,” “catalyst system,” andthe like, can include both heterogeneous compositions and homogenouscompositions.

The terms “chemically-treated solid oxide,” “activator-support,”“treated solid oxide compound,” and the like, are used herein toindicate a solid, inorganic oxide of relatively high porosity, whichexhibits Lewis acidic or Brønsted acidic behavior, and which has beentreated with an electron-withdrawing component, typically an anion, andwhich is calcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, the chemically-treatedsolid oxide compound comprises a calcined contact product of a solidoxide compound with an electron-withdrawing anion source compound.Mixtures or combinations of more than one solid oxide compound and/orelectron-withdrawing anion source compound are contemplated. Typically,the chemically-treated solid oxide comprises at least one ionizing,acidic solid oxide compound. The terms “support” and “activator-support”are not used to imply these components are inert, and such componentsshould not be construed as an inert component of the catalystcomposition.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices, and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

For any particular compound disclosed herein, any structure presentedalso encompasses all conformational isomers, regioisomers, andstereoisomers that may arise from a particular set of substituents. Thestructure also encompasses all enantiomers, diastereomers, and otheroptical isomers whether in enantiomeric or racemic forms, as well asmixtures of stereoisomers, as would be recognized by a skilled artisan.

Applicants disclose several types of ranges in the present invention.These include, but are not limited to, a range of number of atoms, arange of weight ratios, a range of molar ratios, a range oftemperatures, a range of molecular weights, a range of melt indices, arange of densities, a range of catalyst activities, and so forth. WhenApplicants disclose or claim a range of any type, Applicants' intent isto disclose or claim individually each possible number that such a rangecould reasonably encompass, including end points of the range as well asany sub-ranges and combinations of sub-ranges encompassed therein. Forexample, when the Applicants disclose or claim a weight percent of atransition metal compound to a metal-containing sulfatedactivator-support, Applicants' intent is to disclose or claimindividually every possible number that such a range could encompass,consistent with the disclosure herein. By a disclosure that the weightpercent of the transition metal compound to the metal-containingactivator-support is in a range from about 0.01 to about 10 percent,Applicants intend to recite that the weight percent can be selected fromabout 0.01, about 0.02, about 0.03, about 0.04, about 0.05, about 0.06,about 0.07, about 0.08, about 0.09, about 0.1, about 0.2, about 0.3,about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about1, about 1.5, about 2, about 2.5, about 3, about 3.5, about 4, about4.5, about 5, about 5.5, about 6, about 6.5, about 7, about 7.5, about8, about 8.5, about 9, about 9.5, or about 10 percent. Additionally, theweight percent can be within any range from about 0.01 to about 10percent (for example, the weight percent is in a range from about 0.5 toabout 5 percent), and this also includes any combination of rangesbetween about 0.01 and about 10 percent (for example, the weight percentis in a range from about 0.05 to about 1.5 percent or from about 3 toabout 7 percent). Likewise, all other ranges disclosed herein should beinterpreted in a manner similar to this example.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

The terms “a,” “an,” and “the” are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “a solid oxide” or “a metallocene compound”is meant to encompass one, or mixtures or combinations of more than one,solid oxide or metallocene compound, respectively.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps. For example, a metal-containing sulfated activator-support of thepresent invention can comprise, or alternatively, can consistessentially of, a contact product of (i) a transition metal compound;(ii) a sulfate compound; and (iii) a solid oxide.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to metal-containingactivator-supports, catalyst compositions employing these supports,methods for preparing the activator-supports and the catalystcompositions, methods for using the catalyst compositions to polymerizeolefins, the polymer resins produced using such catalyst compositions,and articles produced using these polymer resins. In one aspect, thepresent invention relates to a metal-containing sulfatedactivator-support comprising a contact product of:

(i) a transition metal compound;

(ii) a sulfate compound; and

(iii) a solid oxide.

Such metal-containing sulfated activator-supports can be produced by aprocess which comprises the following steps:

(a) contacting a solid oxide with a sulfate compound to produce asulfated solid oxide;

(b) calcining the sulfated solid oxide to produce a calcined sulfatedsolid oxide; and

(c) contacting the calcined sulfated solid oxide with

-   -   (i) a transition metal compound and a hydrocarbon solvent; or    -   (ii) a vapor comprising a transition metal compound;        to produce the metal-containing sulfated activator-support.

Alternatively, the metal-containing sulfated activator-support can beproduced, for example, by a process comprising:

(a) contacting a solid oxide with a sulfate compound while calcining toproduce a calcined sulfated solid oxide; and

(b) contacting the calcined sulfated solid oxide with

-   -   (i) a transition metal compound and a hydrocarbon solvent; or    -   (ii) a vapor comprising a transition metal compound;        to produce the metal-containing sulfated activator-support.

In either of these processes, a further step optionally can be employedwhich removes the hydrocarbon solvent from the metal-containing sulfatedactivator-support. The present invention also contemplates that themetal-containing sulfated activator-support does not need to be calcinedprior to use in a catalyst composition and polymerization process.

Catalyst compositions of this invention generally comprise a contactproduct of a metallocene compound and a metal-containing sulfatedactivator-support. Often, the catalyst composition also contains anorganoaluminum compound. Catalyst compositions disclosed herein can beused to polymerize olefins. One such process comprises contacting thecatalyst composition with an olefin monomer and optionally an olefincomonomer under polymerization conditions to produce an olefin polymer,wherein the catalyst composition comprises a contact product of ametallocene compound and a metal-containing sulfated activator-support.

Olefin homopolymers, copolymers, terpolymers, and the like, can beproduced using the catalyst compositions and methods for olefinpolymerization disclosed herein. Articles of manufacture can comprisethese polymers, or can be formed from these polymers, and are part ofthis invention.

Catalyst Composition

Catalyst compositions disclosed herein employ a metal-containingsulfated activator-support. According to one aspect of the presentinvention, a catalyst composition is provided which comprises a contactproduct of a metallocene compound and a metal-containing sulfatedactivator-support. The metal-containing sulfated activator-supportcomprises a contact product of:

(i) a transition metal compound;

(ii) a sulfate compound; and

(iii) a solid oxide.

This catalyst composition can further comprise an organoaluminumcompound. These catalyst compositions can be utilized to producepolyolefins, for example, homopolymers, copolymers, or terpolymers, fora variety of end-use applications.

In accordance with this and other aspects of the present invention, itis contemplated that the catalyst compositions disclosed herein cancontain more than one metallocene compound and/or more than oneactivator-support. Additionally, more than one organoaluminum compoundis also contemplated.

In other aspects of this invention, optional co-catalysts can beemployed. For example, a catalyst composition comprising a metallocenecompound and a metal-containing sulfated activator-support can furthercomprise an optional co-catalyst. Suitable co-catalysts in this aspectcan be selected from an aluminoxane compound, an organozinc compound, anorganoboron or organoborate compound, an ionizing ionic compound, andthe like, or combinations thereof. More than one co-catalyst can bepresent in the catalyst composition.

A catalyst composition in another aspect of the present inventioncomprises a contact product of a metallocene compound, ametal-containing sulfated activator-support, and an organoaluminumcompound, wherein this catalyst composition is substantially free ofaluminoxanes, organoboron or organoborate compounds, ionizing ioniccompounds, or other similar co-catalysts. In this aspect, the catalystcomposition has catalyst activity, to be discussed below, in the absenceof these additional materials. For example, a catalyst composition ofthe present invention can consist essentially of a metallocene compound,a metal-containing sulfated activator-support, and an organoaluminumcompound, wherein no other materials are present in the catalystcomposition which would increase/decrease the activity of the catalystcomposition more than about 10% from the catalyst activity of thecatalyst composition in the absence of said materials.

In other aspects of this invention, catalyst compositions comprising acontact product of a metallocene compound and a metal-containingsulfated activator-support can further comprise additionalactivator-supports. For instance, the additional activator-support canbe fluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, and the like, or a combination of these materials.

Alternatively, catalyst compositions of the present invention canfurther comprise an additional activator-support which comprises a solidoxide treated with an electron-withdrawing anion, wherein the solidoxide comprises silica, alumina, silica-alumina, aluminophosphate,heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide, amixed oxide thereof, or any combination thereof. Theelectron-withdrawing anion can be fluoride, chloride, bromide,phosphate, triflate, bisulfate, sulfate, and the like, or combinationsthereof

The additional activator-support employed optionally in a catalystcomposition in accordance with this invention can further comprise ametal or metal ion such as, for example, zinc, titanium, nickel,vanadium, silver, copper, gallium, tin, tungsten, molybdenum, and thelike, or any combination thereof

Yet, in another aspect, catalyst compositions of the present inventioncan further comprise an activator-support selected from a clay mineral,a pillared clay, an exfoliated clay, an exfoliated clay gelled intoanother oxide matrix, a layered silicate mineral, a non-layered silicatemineral, a layered aluminosilicate mineral, a non-layeredaluminosilicate mineral, and the like, or combinations of thesematerials. Additional activator-support materials will be discussed inmore detail below.

This invention further encompasses methods of making catalystcompositions disclosed herein, such as, for example, contacting therespective catalyst components in any order or sequence.

In one aspect of the invention, the metallocene compound can beprecontacted with an olefinic monomer if desired, not necessarily theolefin monomer or comonomer(s) to be polymerized, and an organoaluminumcompound for a first period of time prior to contacting thisprecontacted mixture with an activator-support. The first period of timefor contact, the precontact time, between the metallocene compound theolefinic monomer, and the organoaluminum compound typically ranges froma time period of about 0.05 hours to about 24 hours, for example, fromabout 0.05 hours to about 1 hour. Precontact times from about 10 minutesto about 30 minutes are also employed.

In another aspect of the invention, the metallocene compound can beprecontacted with an olefinic monomer and an activator-support for afirst period of time prior to contacting this precontacted mixture withan organoaluminum compound. The first period of time for contact, theprecontact time, between the metallocene compound, the olefinic monomer,and the activator-support typically ranges from a time period of about0.05 hours to about 24 hours, for example, from about 0.05 hours toabout 2 hours. Precontact times from about 10 minutes to about 60minutes are also employed.

Alternatively, the precontacting process is carried out in multiplesteps, rather than a single step, in which multiple mixtures areprepared, each comprising a different set of catalyst components. Forexample, at least two catalyst components are contacted forming a firstmixture, followed by contacting the first mixture with at least oneother catalyst component forming a second mixture, and so forth.

Multiple precontacting steps can be carried out in a single vessel or inmultiple vessels. Further, multiple precontacting steps can be carriedout in series (i.e., sequentially), in parallel, or a combination ofthese steps. For example, a first mixture of two catalyst components canbe formed in a first vessel, a second mixture comprising the firstmixture plus one additional catalyst component can be formed in thefirst vessel or in a second vessel, which is typically placed downstreamof the first vessel.

In another aspect, one or more of the catalyst components can be splitand used in different precontacting treatments. For example, part of acatalyst component is fed into a first precontacting vessel forprecontacting with at least one other catalyst component, while theremainder of that same catalyst component is fed into a secondprecontacting vessel for precontacting with at least one other catalystcomponent, or is fed directly into the reactor, or a combinationthereof. The precontacting can be carried out in any suitable equipment,such as tanks, stirred mix tanks, various static mixing devices, aflask, a vessel of any type, or combinations of these apparatus.

In another aspect of this invention, the various catalyst components(for example, metallocene, activator-support, organoaluminumco-catalyst, and optionally an unsaturated hydrocarbon) are contacted inthe polymerization reactor simultaneously while the polymerizationreaction is proceeding. Alternatively, any two or more of these catalystcomponents can be precontacted in a vessel prior to entering thereaction zone. This precontacting step can be continuous, in which theprecontacted product is fed continuously to the reactor, or it can be astepwise or batchwise process in which a batch of precontacted productis added to make a catalyst composition. This precontacting step can becarried out over a time period that can range from a few seconds to asmuch as several days, or longer. In this aspect, the continuousprecontacting step generally lasts from about 1 second to about 1 hour.In another aspect, the continuous precontacting step lasts from about 10seconds to about 45 minutes, or from about 1 minute to about 30 minutes.

Once the precontacted mixture of the metallocene compound, olefinmonomer, and organoaluminum co-catalyst is contacted with theactivator-support, this composition (with the addition of theactivator-support) is termed a “postcontacted mixture.” Thepostcontacted mixture optionally remains in contact for a second periodof time, the postcontact time, prior to initiating the polymerizationprocess. Postcontact times between the precontacted mixture and theactivator-support generally range from about 0.05 hours to about 24hours. In a further aspect, the postcontact time is in a range fromabout 0.05 hours to about 1 hour. The precontacting step, thepostcontacting step, or both, can increase the productivity of thepolymer as compared to the same catalyst composition that is preparedwithout precontacting or postcontacting. However, neither aprecontacting step nor a postcontacting step is required.

The postcontacted mixture can be heated at a temperature and for a timeperiod sufficient to allow adsorption, impregnation, or interaction ofprecontacted mixture and the activator-support, such that a portion ofthe components of the precontacted mixture is immobilized, adsorbed, ordeposited thereon. Where heating is employed, the postcontacted mixturegenerally is heated to a temperature of from between about 0° F. toabout 150° F., or from about 40° F. to about 95° F.

In another aspect, the metallocene, organoaluminum, andactivator-support can be precontacted for a period of time prior tobeing contacted with the olefins) to be polymerized in the reactor.

According to one aspect of this invention, the molar ratio of the molesof metallocene compound to the moles of organoaluminum compound in acatalyst composition generally is in a range from about 1:1 to about1:10,000. In another aspect, the molar ratio is in a range from about1:1 to about 1:1,000. Yet, in another aspect, the molar ratio of themoles of metallocene compound to the moles of organoaluminum compound isin a range from about 1:1 to about 1:100. These molar ratios reflect theratio of total moles of metallocene compound or compounds to the totalamount of organoaluminum compound (or compounds) in both theprecontacted mixture and the postcontacted mixture combined, ifprecontacting and/or postcontacting steps are employed.

When a precontacting step is used, the molar ratio of the total moles ofolefin monomer to total moles of metallocene compound in theprecontacted mixture is typically in a range from about 1:10 to about100,000:1. Total moles of each component are used in this ratio toaccount for aspects of this invention where more than one olefin monomerand/or more than metallocene compound are employed. Further, this molarratio can be in a range from about 10:1 to about 1,000:1 in anotheraspect of the invention.

Generally, the weight ratio of organoaluminum compound toactivator-support is in a range from about 10:1 to about 1:1000. If morethan one organoaluminum compound and/or more than one activator-supportare employed, this ratio is based on the total weight of each respectivecomponent. In another aspect, the weight ratio of the organoaluminumcompound to the activator-support is in a range from about 3:1 to about1:100, or from about 1:1 to about 1:50.

In some aspects of this invention, the weight ratio of metallocene toactivator-support is in a range from about 1:1 to about 1:1,000,000. Ifmore than one metallocene and/or more than one activator-support areemployed, this ratio is based on the total weight of each respectivecomponent. In another aspect, this weight ratio is in a range from about1:5 to about 1:100,000, or from about 1:10 to about 1:10,000. Yet, inanother aspect, the weight ratio of the metallocene compound to theactivator-support is in a range from about 1:20 to about 1:1000.

In yet another aspect of this invention, the concentration of themetallocene, in units of micromoles of the metallocene per gram of theactivator-support, is in a range from about 0.5 to about 150. If morethan one metallocene and/or more than one activator-support is employed,this ratio is based on the total weight of each respective component. Inanother aspect, the concentration of the metallocene, in units ofmicromoles of the metallocene per gram of the activator-support, is in arange from about 1 to about 120, for example, from about 5 to about 100,from about 5 to about 80, from about 5 to about 60, or from about 5 toabout 40. In still another aspect, the concentration of the metallocene,in units of micromoles of the metallocene per gram of theactivator-support, is in a range from about 5 to about 20.

According to some aspects of this invention, aluminoxane compounds arenot required to form the catalyst composition. Thus, the polymerizationcan proceed in the absence of aluminoxanes. Accordingly, the presentinvention can use, for example, organoaluminum compounds and anactivator-support in the absence of aluminoxanes. While not intending tobe bound by theory, it is believed that the organoaluminum compoundlikely does not activate the metallocene catalyst in the same manner asan organoaluminoxane compound.

Additionally, in some aspects, organoboron and organoborate compoundsare not required to form a catalyst composition of this invention.Nonetheless, aluminoxanes, organoboron or organoborate compounds,ionizing ionic compounds, or combinations thereof, optionally can beused in other catalyst compositions contemplated by and encompassedwithin the present invention. Hence, co-catalysts such as aluminoxanes,organozinc compounds, organoboron or organoborate compounds, ionizingionic compounds, or combinations thereof, can be employed with themetallocene compound and activator-support, for example, either in thepresence or in the absence of an organoaluminum compound.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 100 grams of olefin polymer (homopolymer,copolymer, etc., as the context requires) per gram of activator-supportper hour (i.e., metal-containing sulfated activator-support). Thisactivity is abbreviated as gP/gAS/hr. In another aspect, the catalystactivity is greater than about 150, greater than about 200, or greaterthan about 250 gP/gAS/hr. In still another aspect, catalyst compositionsof this invention are characterized by having a catalyst activitygreater than about 500, greater than about 1000, or greater than about1500 gP/gAS/hr. Yet, in another aspect, the catalyst activity is greaterthan about 2000 gP/gAS/hr. This activity is measured under slurrypolymerization conditions using isobutane as the diluent, at apolymerization temperature of about 90° C. and a reactor pressure ofabout 400 psig. The reactor pressure is largely controlled by thepressure of the monomer, e.g., the ethylene pressure, but othercontributors to the reactor pressure include hydrogen gas (if hydrogenis used), isobutane vapor, and comonomer gas or vapor (if a comonomer isused).

Generally, catalyst compositions of the present invention have acatalyst activity greater than about 25,000 grams of olefin polymer pergram of metallocene per hour (abbreviated gP/gMET/hr). For example, thecatalyst activity can be greater than about 30,000, greater than about40,000, or greater than about 50,000 gP/gMET/hr. In another aspect,catalyst compositions of this invention are characterized by having acatalyst activity greater than about 75,000, greater than about 100,000,or greater than about 125,000 gP/gMET/hr. In still another aspect ofthis invention, the catalyst activity can be greater than about 150,000,or greater than about 200,000 gP/gMET/hr. This activity is measuredunder slurry polymerization conditions using isobutane as the diluent,at a polymerization temperature of about 90° C. and a reactor pressureof about 400 psig.

As discussed above, any combination of the metallocene compound, theactivator-support, the organoaluminum compound, and the olefin monomer,can be precontacted in some aspects of this invention. When anyprecontacting occurs with an olefinic monomer, it is not necessary thatthe olefin monomer used in the precontacting step be the same as theolefin to be polymerized. Further, when a precontacting step among anycombination of the catalyst components is employed for a first period oftime, this precontacted mixture can be used in a subsequentpostcontacting step between any other combinations of catalystcomponents for a second period of time. For example, a metallocenecompound, an organoaluminum compound, and 1-hexene can be used in aprecontacting step for a first period of time, and this precontactedmixture then can be contacted with an activator-support to form apostcontacted mixture that is contacted for a second period of timeprior to initiating the polymerization reaction. For example, the firstperiod of time for contact, the precontact time, between any combinationof the metallocene compound, the olefinic monomer, theactivator-support, and the organoaluminum compound can be from about0.05 hours to about 24 hours, from about 0.05 hours to about 1 hour, orfrom about 10 minutes to about 30 minutes. The postcontacted mixtureoptionally is allowed to remain in contact for a second period of time,the postcontact time, prior to initiating the polymerization process.According to one aspect of this invention, postcontact times between theprecontacted mixture and any remaining catalyst components is from about0.05 hours to about 24 hours, or from about 0.1 hour to about 1 hour.

Metal-Containing Sulfated Activator-Support

A metal-containing sulfated activator-support of this inventioncomprises a contact product of:

(i) a transition metal compound;

(ii) a sulfate compound; and

(iii) a solid oxide.

Generally, the transition metal compound used to produce themetal-containing sulfated activator-support can be any compound whichcontains a transition metal from Groups 3 to 11 of the periodic table.For example, transition metal compounds containing titanium, zirconium,hafnium, vanadium, molybdenum, tungsten, iron, cobalt, nickel, copper,scandium, yttrium, lanthanum, and the like, or combinations thereof, canbe employed in the present invention. In some aspects of this invention,the transition metal can be titanium, zirconium, hafnium, vanadium,nickel, or a lanthanide. The metal-containing sulfated activator-supportcan comprise titanium, zirconium, hafnium, or vanadium, or combinationsthereof, in other aspects of this invention. Representative transitionmetal compounds which can be employed include, but are not limited to,TiCl₄, Zr(NMe₂)₄, VOCl₃, tetrabenzyl zirconium, ZrOBuCl₃, tetraneopentylzirconium, VCl₄, V(OBu)₂, V(OBu)₂Cl₂, VO(OBu)Cl₂, Ti(OBu)₂Cl₂,Ti(OBu)₂Cl₂, Ti(OCHMe₂)Cl₂, Ti(OBu)Cl₃, Ti(OCHMe₂)Cl₃, Ti(allyl)₂, Ti(O)cyclo-octadiene, Ti(O) cyclo-octatetraene, Ti(CH₂Si(CH₃)₃)₂,bis-dimethylpentadienyl titanium, bis-dimethylpentadienyl vanadium,vanadocene, and the like, or combinations or mixtures thereof.

The amount of the transition metal compound used to prepare themetal-containing sulfated activator-support typically falls within arange from about 0.01 to about 15 weight percent, based on the weight ofthe metal-containing activator-support. In one aspect, the weightpercent of the transition metal compound to the metal-containingsulfated activator-support is in a range from about 0.01 to about 10percent. In other aspects, the weight percent of the transition metalcompound to the metal-containing sulfated activator-support is in arange from about 0.1 to about 9 percent, from about 0.1 to about 5percent, from about 0.1 to about 3 percent, or from about 0.3 to about 2percent.

The solid oxide used to produce the metal-containing sulfatedactivator-support can comprise a solid inorganic oxide comprising oxygenand at least one element selected from Groups 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, or 15 of the periodic table, or comprising oxygenand at least one element selected from the lanthanide or actinideelements (See: Hawley's Condensed Chemical Dictionary, 11^(th) Ed., JohnWiley & Sons, 1995; Cotton, F. A., Wilkinson, G., Murillo, C. A., andBochmann, M., Advanced Inorganic Chemistry, 6^(th) Ed.,Wiley-Interscience, 1999). For example, the inorganic oxide can compriseoxygen and at least one element selected from Al, B, Be, Bi, Cd, Co, Cr,Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn, andZr.

Accordingly, suitable examples of solid oxide materials or compoundsthat can be used to form the metal-containing sulfated activator-supportinclude, but are not limited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄,Cr₂O₃, CuO, Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂,SnO₂, SrO, ThO₂, TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like,including mixed oxides thereof, and combinations thereof. This includesco-gels or co-precipitates of different solid oxide materials. Inaccordance with one aspect of this invention, the solid oxide comprisessilica, alumina, silica-alumina, aluminophosphate, titania, zirconia,magnesia, boria, zinc oxide, any mixed oxide thereof, or any combinationthereof. In another aspect, the solid oxide comprises alumina or silica,for instance, silica-alumina, aluminophosphate, or alumina. Yet, inanother aspect, the solid oxide is alumina. Solid oxides which can beemployed in the metal-containing sulfated activator-support, or can beused to form chemically-treated solid oxides which can be used as anoptional component in a catalyst composition, are discussed in furtherdetail below.

Solid oxides of the present invention generally have surface areasranging from about 100 to about 1000 m²/g. In some aspects, the surfacearea falls within a range from about 150 to about 750 m²/g, for example,from about 200 to about 600 m²/g. The surface area of the solid oxidecan range from about 250 to about 500 m²/g in another aspect of thisinvention. Solid oxides having surface areas of about 300 m²/g, about350 m²/g, about 400 m²/g, or about 450 m²/g, can be employed in thisinvention.

The pore volume of the solid oxide is generally greater than about 0.5mL/g Often, the pore volume is greater than about 0.75 mL/g, or greaterthan about 1 mL/g. In another aspect, the pore volume is greater thanabout 1.2 mL/g. In yet another aspect, the pore volume falls within arange from about 0.8 mL/g to about 1.8 mL/g, such as, for example, fromabout 1 mL/g to about 1.6 mL/g

The solid oxides disclosed herein generally have average particle sizesranging from about 10 microns to about 200 microns. In some aspects ofthis invention, the average particle size falls within a range fromabout 25 microns to about 150 microns. For example, the average particlesize of the solid oxide can be in a range from about 40 to about 120microns.

In accordance with the present invention, metal-containing sulfatedactivator-supports comprise a contact product of (i) a transition metalcompound; (ii) a sulfate compound; and (iii) a solid oxide. The sulfatecompound is an electron-withdrawing anion source compound and,correspondingly, the electron-withdrawing anion is sulfate. Illustrativeand non-limiting examples of suitable sulfate compounds include H₂SO₄,(NH₄)₂SO₄, NH₄HSO₄, Al₂(SO)₃, SO₃ gas, organics sulfates, metal sulfates(e.g., titanium, vanadium, copper, zinc, lanthanum, etc.), and the like,or a combination of these sulfate sources. Sulfuric acid and/or ammoniumsulfate is/are often used as the sulfate compound.

A process of the present invention to produce a metal-containingsulfated activator-support can comprise the following steps:

(a) contacting a solid oxide with a sulfate compound to produce asulfated solid oxide;

(b) calcining the sulfated solid oxide to produce a calcined sulfatedsolid oxide; and

(c) contacting the calcined sulfated solid oxide with

-   -   (i) a transition metal compound and a hydrocarbon solvent; or    -   (ii) a vapor comprising a transition metal compound;        to produce the metal-containing sulfated activator-support.

Also encompassed by this invention is a metal-containing sulfatedactivator-support produced by this process. Prior to step (a) of thisprocess, the solid oxide can be calcined, although this is not arequirement. If the solid oxide is calcined, the calcining is conductedtypically at a temperature from about 400° C. to about 800° C. for atime period ranging from about 30 minutes to about 20 hours. In step(a), the solid oxide and the sulfate compound are contacted. Forinstance, the solid oxide can be alumina and the sulfate compound can besulfuric acid or a sulfate salt, such as ammonium sulfate. The sulfatedsolid oxide of step (a) can be produced by forming a slurry of the solidoxide in a suitable solvent, such as alcohol or water, in which thedesired concentration of the sulfating agent has been added. Suitableorganic solvents include, but are not limited to, the one to threecarbon alcohols because of their volatility and low surface tension.Alternatively, the solid oxide can be contacted with sulfate in the gasphase.

According to one aspect of this invention, a weight ratio of the sulfatecompound to the solid oxide is in a range from about 1:100 to about 1:1.According to another aspect of this invention, the weight ratio of thesulfate compound to the solid oxide is in a range from about 1:75 toabout 1:2, from about 1:50 to about 1:3, or from about 1:20 to about1:4.

In another aspect, the ratio of the sulfate compound to the solid oxideis greater than about 0.5 mmol/g. Often, the ratio of the sulfatecompound to the solid oxide is greater than about 1 mmol/g, or greaterthan about 1.5 mmol/g. For example, the ratio of the sulfate compound tothe solid oxide can be in a range from about 1.5 mmol/g to about 10mmol/g.

Once impregnated with sulfate, the sulfated solid oxide can be dried byany suitable method including, but not limited to, suction filtrationfollowed by evaporation, drying under vacuum, spray drying, and thelike, although it is also possible to initiate the calcining stepimmediately without drying. Calcining the sulfated solid oxide toproduce a calcined sulfated solid oxide, step (b) above, generally isconducted in an ambient atmosphere, typically in a dry ambientatmosphere, at a temperature from about 300° C. to about 900° C., andfor a time of about 1 minute to about 30 hours. Calcining can beconducted at a temperature from about 400° C. to about 800° C., oralternatively, at a temperature from about 500° C. to about 700° C.Calcining can be conducted for about 5 minutes to about 24 hours, or forabout 15 minutes to about 10 hours. Thus, for example, calcining can becarried out for about 3 to about 10 hours at a temperature from about450° C. to about 650° C. Alternatively, calcining can be conducted forabout 0.5 to about 8 hours at a temperature in a range from about 500°C. to about 700° C. In another aspect, calcining can be conducted at atemperature in a range from about 350° C. to about 600° C. for a timeperiod ranging from about 0.3 to about 20 hours. Generally, calcining isconducted in an oxidizing atmosphere, such as air or oxygen.Alternatively, an inert atmosphere, such as nitrogen or argon, or a wetatmosphere, such as steam, can be used. Additional information oncalcining is provided below in the discussion of additionalactivator-supports.

In step (c) of this process, the transition metal is deposited onto thecalcined sulfated solid oxide. In the (c)(i) alternative, the calcinedsulfated solid oxide is contacted with a transition metal compound and ahydrocarbon solvent to produce the metal-containing sulfatedactivator-support. The calcined sulfated solid oxide can be contactedwith a mixture comprising the hydrocarbon solvent and the transitionmetal compound, and this mixture can be a solution or a slurry. Forexample, this process contemplates transition metal compounds which arecompletely soluble, partially soluble, or completely insoluble in thehydrocarbon solvent. In another aspect, the calcined sulfated solidoxide is slurried in a hydrocarbon solvent, to which the transitionmetal compound is then added. Therefore, various orders of contactingthe calcined sulfated solid oxide, the transition metal compound, andthe hydrocarbon solvent are contemplated herein and, accordingly, allorders of additions are encompassed by this invention. It is alsocontemplated, for instance, that the calcined sulfated solid oxidecompound is contacted with the metallocene compound prior to contactingwith the transition metal compound, although often the metal-containingsulfated activator-support is formed first, and then contacted with themetallocene compound. In still another aspect, the metallocene compoundand a mixture comprising a transition metal compound and a hydrocarbonsolvent are continuously added to a vessel into which the calcinedsulfated solid oxide is also continuously fed. After a certain contactor residence time, which can vary from one minute to several hours ormore, this mixture or slurry can be fed continuously to a polymerizationreactor.

Transition metal compounds which contain titanium, zirconium, hafnium,vanadium, molybdenum, tungsten, iron, cobalt, nickel, copper, scandium,yttrium, lanthanum, and the like, or combinations of transition metalcompounds, can be employed in step (c) of the process. Examples ofsuitable hydrocarbon solvents include, but are not limited to, propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane,n-hexane, and n-heptane. In some aspects of this invention, thehydrocarbon solvent is a straight chain saturated hydrocarbon such asn-pentane, n-hexane, and n-heptane, for example.

The metal-containing sulfated activator-support produced in step (c) maybe wet and, therefore, the hydrocarbon solvent optionally can be removedfrom the metal-containing sulfated activator-support. The optionaldrying step can be performed under vacuum or an inert atmosphere. Dryingthe metal-containing sulfated activator-support is not required,however. The metal-containing sulfated activator-support, whether wet ordry, can be utilized as a part of a catalyst composition withoutadditional processing. For instance, the metal-containing sulfatedactivator-support does not need to be calcined prior to being used in acatalyst composition, for instance, to polymerize olefins. Hence, in oneaspect of this invention, the metal-containing sulfatedactivator-support produced in step (c) is not subsequently calcined.

In the (c)(ii) alternative, the calcined sulfated solid oxide iscontacted with a vapor comprising a transition metal compound to producethe metal-containing sulfated activator-support. In this aspect, thetransition metal is deposited onto the calcined sulfated solid oxide inthe vapor/gas phase. Often, this is accomplished by employing atransition metal compound which is available as a liquid, and injectingthis liquid into a gas/vapor stream which is used to fluidize thecalcined sulfated solid oxide. The liquid transition metal compound canevaporate and contact the calcined sulfated solid oxide as part of thefluidizing gas/vapor. A non-limiting example of a transition metalcompound which can be contacted with the calcined sulfated solid oxidein this manner is TiCl₄. Temperatures employed in step (c)(ii) of thisprocess generally fall within a range from about 25° C. to about 300° C.

Another process than can be employed to produce a metal-containingsulfated activator-support comprises:

(a) contacting a solid oxide with a sulfate compound while calcining toproduce a calcined sulfated solid oxide; and

(b) contacting the calcined sulfated solid oxide with

-   -   (i) a transition metal compound and a hydrocarbon solvent; or    -   (ii) a vapor comprising a transition metal compound;        to produce the metal-containing sulfated activator-support.

This invention also encompasses a metal-containing sulfatedactivator-support produced by this process. As with the alternateprocess described above, prior to step (a) of this process, the solidoxide can be calcined, but this is not a requirement. In step (a), thesolid oxide and the sulfate compound can be contacted simultaneously orconcurrently while calcining Contacting can be in an aqueoussolution/slurry, an anhydrous solution/slurry (e.g., in alcohol), or inthe gas phase. Calcining conditions, both time and temperature, can fallwithin the ranges provided above.

In step (b), the calcined sulfated solid oxide is contacted with either(i) a transition metal compound and a hydrocarbon solvent, or (ii) avapor comprising a transition metal compound, to produce themetal-containing sulfated activator-support. Representative transitionmetals, metal compounds, and hydrocarbon solvents provided above alsocan be utilized in this process. The resultant metal-containing sulfatedactivator-support of step (b) may be wet and, optionally, thehydrocarbon solvent can be removed from the metal-containing sulfatedactivator-support. The metal-containing sulfated activator-support doesnot need to be calcined prior to being used in a catalyst composition,and in one aspect of this invention, the metal-containing sulfatedactivator-support produced in step (b) is not subsequently calcined.

Metal-containing sulfated activator-supports produced in accordance withthis invention generally have surface areas ranging from about 100 toabout 1000 m²/g. In some aspects, the surface area falls within a rangefrom about 150 to about 750 m²/g, for example, from about 200 to about600 m²/g. The surface area of the metal-containing sulfatedactivator-support can range from about 250 to about 500 m²/g in anotheraspect of this invention. For instance, metal-containing sulfatedactivator-supports having surface areas of about 300 m²/g, about 350m²/g, about 400 m²/g, or about 450 m²/g, can be employed in thisinvention.

The pore volume of the metal-containing sulfated activator-support isgenerally greater than about 0.5 mL/g Often, the pore volume is greaterthan about 0.7 mL/g, or greater than about 1 mL/g. In another aspect,the pore volume is greater than about 1.3 mL/g. In yet another aspect,the pore volume falls within a range from about 0.8 mL/g to about 1.8mL/g, such as, for example, from about 1 mL/g to about 1.6 mL/g

Generally, the average pore size of the metal-containing sulfatedactivator-support is greater than about 50 angstroms. For instance, theaverage pore size can be greater than about 80, greater than about 90,or greater than about 100 angstroms. In one aspect, the average poresize is within a range from about 100 to about 200 angstroms.

The metal-containing sulfated activator-supports disclosed hereingenerally have average particle sizes ranging from about 5 microns toabout 200 microns. In some aspects of this invention, the averageparticle size falls within a range from about 10 microns to about 200microns, or from about 25 microns to about 150 microns. For example, theaverage particle size of metal-containing sulfated activator-support canbe in a range from about 40 to about 120 microns, or from about 40 toabout 80 microns.

Additional Activator-Supports

The present invention encompasses various catalyst compositions whichcan include a metal-containing sulfated activator-support. For example,a catalyst composition is provided which comprises a contact product ofa metallocene compound and a metal-containing sulfatedactivator-support. The metal-containing sulfated activator-supportcomprises a contact product of (i) a transition metal compound; (ii) asulfate compound; and (iii) a solid oxide.

Such catalyst compositions can further comprise an additionalactivator-support, such as a chemically-treated solid oxide, that isdifferent from the metal-containing sulfated activator-support of thepresent invention. Alternatively, the catalyst composition can furthercomprise an activator-support selected from a clay mineral, a pillaredclay, an exfoliated clay, an exfoliated clay gelled into another oxidematrix, a layered silicate mineral, a non-layered silicate mineral, alayered aluminosilicate mineral, a non-layered aluminosilicate mineral,and the like, or any combination thereof.

Generally, chemically-treated solid oxides exhibit enhanced acidity ascompared to the corresponding untreated solid oxide compound. Thechemically-treated solid oxide also functions as a catalyst activator ascompared to the corresponding untreated solid oxide. While thechemically-treated solid oxide activates the metallocene in the absenceof co-catalysts, it is not necessary to eliminate co-catalysts from thecatalyst composition. The activation function of the activator-supportis evident in the enhanced activity of catalyst composition as a whole,as compared to a catalyst composition containing the correspondinguntreated solid oxide. However, it is believed that thechemically-treated solid oxide can function as an activator, even in theabsence of organoaluminum compounds, aluminoxanes, organoboroncompounds, ionizing ionic compounds, and the like.

Chemically-treated solid oxides comprise at least one solid oxidetreated with at least one electron-withdrawing anion. While notintending to be bound by the following statement, it is believed thattreatment of the solid oxide with an electron-withdrawing componentaugments or enhances the acidity of the oxide. Thus, either theactivator-support exhibits Lewis or Brønsted acidity that is typicallygreater than the Lewis or Brønsted acid strength of the untreated solidoxide, or the activator-support has a greater number of acid sites thanthe untreated solid oxide, or both. One method to quantify the acidityof the chemically-treated and the untreated solid oxide materials is bycomparing the polymerization activities of the treated and the untreatedoxides under acid catalyzed reactions.

Chemically-treated solid oxides of this invention are formed generallyfrom an inorganic solid oxide that exhibits Lewis acidic or Brønstedacidic behavior and has a relatively high porosity. The solid oxide ischemically-treated with an electron-withdrawing component, typically anelectron-withdrawing anion, to form an activator-support.

The pore volume and surface area of solid oxides were discussed in thepreceding section. Solid oxides used to prepare an additionalchemically-treated solid oxide generally have a pore volume greater thanabout 0.1 mL/g According to another aspect of the present invention, thesolid oxide has a pore volume greater than about 0.5 mL/g According toyet another aspect of the present invention, the solid oxide has a porevolume greater than about 1 mL/g.

In another aspect, the solid oxide used to prepare the additionalchemically-treated solid oxide has a surface area ranging from about 100to about 1000 m²/g, for example, in a range from about 200 to about 800m²/g. In still another aspect of the present invention, the solid oxidehas a surface area in a range from about 250 to about 600 m²/g.

In still another aspect, the optional chemically-treated solid oxide cancomprise a solid inorganic oxide comprising oxygen and at least oneelement selected from Group 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,or 15 of the periodic table, or comprising oxygen and at least oneelement selected from the lanthanide or actinide elements (See: Hawley'sCondensed Chemical Dictionary, 11^(th) Ed., John Wiley & Sons, 1995;Cotton, F. A., Wilkinson, G., Murillo, C. A., and Bochmann, M., AdvancedInorganic Chemistry, 6^(th) Ed., Wiley-Interscience, 1999). For example,the inorganic oxide can comprise oxygen and at least one elementselected from Al, B, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb,Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn or Zr.

Suitable examples of solid oxide materials or compounds that can be usedto form the additional chemically-treated solid oxide include, but arenot limited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO, Fe₂O₃,Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂,TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixed oxidesthereof, and combinations thereof. For example, the solid oxide that canbe used to prepare the additional chemically-treated solid oxide can besilica, alumina, silica-alumina, aluminum phosphate,heteropolytungstate, titania, zirconia, magnesia, boria, zinc oxide,mixed oxides thereof, or any combination thereof.

Solid oxides of this invention, which can be used to prepare additionalchemically-treated solid oxides, encompass oxide materials such asalumina, “mixed oxide” compounds thereof such as silica-alumina, andcombinations and mixtures thereof. The mixed oxides such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form a solid oxide. Examples of mixedoxides that can be used in the additional, optional activator-support ofthe present invention include, but are not limited to, silica-alumina,silica-titania, silica-zirconia, zeolites, various clay minerals,alumina-titania, alumina-zirconia, zinc-aluminate, and the like.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspectof the present invention, the electron-withdrawing component is anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Examples of electron-withdrawing anionsinclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, including mixtures and combinationsthereof. In addition, other ionic or non-ionic compounds that serve assources for these electron-withdrawing anions also can be employed inthe present invention.

Thus, for example, the additional chemically-treated solid oxideoptionally used in the catalyst compositions of the present inventioncan be fluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, and the like, or combinations thereof.

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt can beselected from any cation that allows the salt to revert or decomposeback to the acid during calcining Factors that dictate the suitabilityof the particular salt to serve as a source for the electron-withdrawinganion include, but are not limited to, the solubility of the salt in thedesired solvent, the lack of adverse reactivity of the cation,ion-pairing effects between the cation and anion, hygroscopic propertiesimparted to the salt by the cation, and the like, and thermal stabilityof the anion. Examples of suitable cations in the salt of theelectron-withdrawing anion include, but are not limited to, ammonium,trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H⁺,[H(OEt₂)₂]⁺, and the like.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron-withdrawing components can be contacted with the oxide materialsimultaneously or individually, and in any order that affords thedesired chemically-treated solid oxide acidity. For example, one aspectof this invention is employing two or more electron-withdrawing anionsource compounds in two or more separate contacting steps.

Thus, one example of such a process by which a chemically-treated solidoxide is prepared is as follows: a selected solid oxide, or combinationof oxides, is contacted with a first electron-withdrawing anion sourcecompound to form a first mixture; this first mixture is calcined andthen contacted with a second electron-withdrawing anion source compoundto form a second mixture; the second mixture is then calcined to form atreated solid oxide. In such a process, the first and secondelectron-withdrawing anion source compounds are either the same ordifferent compounds.

According to another aspect of the present invention, the additionalchemically-treated solid oxide comprises a solid inorganic oxidematerial, a mixed oxide material, or a combination of inorganic oxidematerials, that is chemically-treated with an electron-withdrawingcomponent, and optionally treated with a metal source, including metalsalts, metal ions, or other metal-containing compounds. Non-limitingexamples of the metal or metal ion include zinc, nickel, vanadium,titanium, silver, copper, gallium, tin, tungsten, molybdenum, and thelike, or combinations thereof.

Various processes are used to form chemically-treated solid oxidesuseful in the present invention. The chemically-treated solid oxide cancomprise the contact product of a solid oxide and anelectron-withdrawing anion source. It is not required that the solidoxide be calcined prior to contacting the electron-withdrawing anionsource. The contact product typically is calcined either during or afterthe solid oxide compound is contacted with the electron-withdrawinganion source. The solid oxide can be calcined or uncalcined. Variousprocesses to prepare solid oxide activator-supports that can be employedin this invention have been reported. For example, such methods aredescribed in U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271,6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666,6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894,6,667,274, and 6,750,302, the disclosures of which are incorporatedherein by reference in their entirety.

The method by which the solid oxide is contacted with theelectron-withdrawing component, typically a salt or an acid of anelectron-withdrawing anion, can include, but is not limited to, gelling,co-gelling, impregnation of one compound onto another, and the like.Thus, following any contacting method, the contacted mixture of thesolid oxide and electron-withdrawing anion is calcined.

The optional solid oxide activator-support (i.e., chemically-treatedsolid oxide) thus can be produced by a process comprising:

1) contacting a solid oxide with an electron-withdrawing anion sourcecompound to form a first mixture; and

2) calcining the first mixture to form the solid oxideactivator-support.

According to another aspect of the present invention, the solid oxideactivator-support (chemically-treated solid oxide) is produced by aprocess comprising:

1) contacting a solid oxide with a first electron-withdrawing anionsource compound to form a first mixture;

2) calcining the first mixture to produce a calcined first mixture;

3) contacting the calcined first mixture with a secondelectron-withdrawing anion source compound to form a second mixture; and

4) calcining the second mixture to form the solid oxideactivator-support.

According to yet another aspect of the present invention, thechemically-treated solid oxide is produced or formed by contacting thesolid oxide with the electron-withdrawing anion source compound, wherethe solid oxide compound is calcined before, during, or after contactingthe electron-withdrawing anion source.

Calcining of the treated solid oxide generally is conducted in anambient atmosphere, typically in a dry ambient atmosphere, at atemperature from about 200° C. to about 900° C., and for a time of about1 minute to about 100 hours. Calcining can be conducted at a temperaturefrom about 300° C. to about 800° C., or alternatively, at a temperaturefrom about 400° C. to about 700° C. Calcining can be conducted for about30 minutes to about 50 hours, or for about 1 hour to about 15 hours.Thus, for example, calcining can be carried out for about 3 to about 10hours at a temperature from about 350° C. to about 550° C. Any suitableambient atmosphere can be employed during calcining. Generally,calcining is conducted in an oxidizing atmosphere, such as air oroxygen. Alternatively, an inert atmosphere, such as nitrogen or argon,or a reducing atmosphere, such as hydrogen or carbon monoxide, can beused.

According to one aspect of the present invention, the solid oxidematerial is treated with a source of halide ion, sulfate ion, or acombination of anions, and then calcined to provide thechemically-treated solid oxide in the form of a particulate solid. Forexample, the solid oxide material is treated with a source of sulfate(termed a “sulfating agent”), a source of chloride ion (termed a“chloriding agent”), a source of fluoride ion (termed a “fluoridingagent”), or a combination thereof, and calcined to provide the solidoxide activator. Exemplary additional, or optional, activator-supportsthat can be employed in catalyst compositions of the present inventioninclude, but are not limited to, bromided alumina, chlorided alumina,fluorided alumina, sulfated alumina, bromided silica-alumina, chloridedsilica-alumina, fluorided silica-alumina, sulfated silica-alumina,bromided silica-zirconia, chlorided silica-zirconia, fluoridedsilica-zirconia, sulfated silica-zirconia; a pillared clay, such as apillared montmorillonite, optionally treated with fluoride, chloride, orsulfate; phosphated alumina or other aluminophosphates optionallytreated with sulfate, fluoride, or chloride; or any combination of theabove.

A chemically-treated solid oxide can comprise a fluorided solid oxide inthe form of a particulate solid. The fluorided solid oxide can be formedby contacting a solid oxide with a fluoriding agent. The fluoride ioncan be added to the oxide by forming a slurry of the oxide in a suitableorganic or aqueous solvent, such as alcohol or water including, but notlimited to, the one to three carbon alcohols because of their volatilityand low surface tension. Examples of suitable fluoriding agents include,but are not limited to, hydrofluoric acid (HF), ammonium fluoride(NH₄F), ammonium bifluoride (NH₄HF₂), ammonium tetrafluoroborate(NH₄BF₄), ammonium silicofluoride (hexafluorosilicate) ((NH₄)₂SiF₆),ammonium hexafluorophosphate (NH₄PF₆), hexafluorotitanic acid (H₂TiF₆),ammonium hexafluorotitanic acid ((NH₄)₂TiF₆), hexafluorozirconic acid(H₂ZrF₆), analogs thereof, and combinations thereof. For example,ammonium bifluoride (NH₄HF₂) can be used as the fluoriding agent, due toits ease of use and availability.

If desired, the solid oxide is treated with a fluoriding agent duringthe calcining step. Any fluoriding agent capable of thoroughlycontacting the solid oxide during the calcining step can be used. Forexample, in addition to those fluoriding agents described previously,volatile organic fluoriding agents can be used. Examples of volatileorganic fluoriding agents useful in this aspect of the inventioninclude, but are not limited to, freons, perfluorohexane,perfluorobenzene, fluoromethane, trifluoroethanol, an the like, andcombinations thereof. Calcining temperatures generally must be highenough to decompose the compound and release fluoride. Gaseous hydrogenfluoride (HF) or fluorine (F₂) itself also can be used with the solidoxide if fluorided while calcining. Silicon tetrafluoride (SiF₄) andcompounds containing tetrafluoroborate (BF₄) can also be employed. Oneconvenient method of contacting the solid oxide with the fluoridingagent is to vaporize a fluoriding agent into a gas stream used tofluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically-treatedsolid oxide comprises a chlorided solid oxide in the form of aparticulate solid. The chlorided solid oxide is formed by contacting asolid oxide with a chloriding agent. The chloride ion can be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Thesolid oxide can be treated with a chloriding agent during the calciningstep. Any chloriding agent capable of serving as a source of chlorideand thoroughly contacting the oxide during the calcining step can beused. For example, volatile organic chloriding agents can be used.Examples of suitable volatile organic chloriding agents include, but arenot limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, andthe like, or any combination thereof. Gaseous hydrogen chloride orchlorine itself also can be used with the solid oxide during calcining.One convenient method of contacting the oxide with the chloriding agentis to vaporize a chloriding agent into a gas stream used to fluidize thesolid oxide during calcination.

The amount of fluoride or chloride ion present before calcining thesolid oxide generally is from about 1 to about 50% by weight, whereweight percent is based on the weight of the solid oxide, for example,silica-alumina, before calcining According to another aspect of thisinvention, the amount of fluoride or chloride ion present beforecalcining the solid oxide is from about 1 to about 25% by weight, fromabout 2 to about 15%, or from about 3% to about 12% by weight. Accordingto yet another aspect of this invention, the amount of fluoride orchloride ion present before calcining the solid oxide is from about 5 toabout 10% by weight. Once impregnated with halide, the halided oxide canbe dried by any suitable method including, but not limited to, suctionfiltration followed by evaporation, drying under vacuum, spray drying,and the like, although it is also possible to initiate the calciningstep immediately without drying the impregnated solid oxide.

The silica-alumina which can be used in the present invention typicallyhas an alumina content from about 5% to about 95% by weight. Accordingto one aspect of this invention, the alumina content of thesilica-alumina is from about 5% to about 50%, or from about 8% to about30%, alumina by weight. In another aspect, high alumina contentsilica-alumina compounds can be employed, in which the alumina contentof these silica-alumina compounds typically ranges from about 60% toabout 90%, or from about 65% to about 80%, alumina by weight. Accordingto yet another aspect of this invention, the solid oxide componentcomprises alumina without silica, and according to another aspect ofthis invention, the solid oxide component comprises silica withoutalumina

A sulfated solid oxide comprises sulfate and a solid oxide component,such as alumina or silica-alumina, in the form of a particulate solid.According to one aspect of the present invention, the sulfated solidoxide comprises sulfate and alumina. In some instances, the sulfatedalumina is formed by a process wherein the alumina is treated with asulfate source, for example, sulfuric acid or a sulfate salt such asammonium sulfate. This process is generally performed by forming aslurry of the alumina in a suitable solvent, such as alcohol or water,in which the desired concentration of the sulfating agent has beenadded. Suitable organic solvents include, but are not limited to, theone to three carbon alcohols because of their volatility and low surfacetension.

According to one aspect of this invention, the amount of sulfate ionpresent before calcining is from about 0.5 to about 100 parts by weightsulfate ion to about 100 parts by weight solid oxide. According toanother aspect of this invention, the amount of sulfate ion presentbefore calcining is from about 1 to about 50 parts by weight sulfate ionto about 100 parts by weight solid oxide, and according to still anotheraspect of this invention, from about 5 to about 30 parts by weightsulfate ion to about 100 parts by weight solid oxide. These weightratios are based on the weight of the solid oxide before calcining. Onceimpregnated with sulfate, the sulfated oxide can be dried by anysuitable method including, but not limited to, suction filtrationfollowed by evaporation, drying under vacuum, spray drying, and thelike, although it is also possible to initiate the calcining stepimmediately.

According to another aspect of the present invention, the catalystcomposition further comprises an ion-exchangeable activator-support,including but not limited to silicate and aluminosilicate compounds orminerals, either with layered or non-layered structures, andcombinations thereof. In another aspect of this invention,ion-exchangeable, layered aluminosilicates such as pillared clays areused as optional activator-supports. The ion-exchangeableactivator-support optionally can be treated with at least oneelectron-withdrawing anion such as those disclosed herein, thoughtypically the ion-exchangeable activator-support is not treated with anelectron-withdrawing anion.

According to another aspect of the present invention, the catalystcomposition further comprises clay minerals having exchangeable cationsand layers capable of expanding. Typical clay mineral activator-supportsinclude, but are not limited to, ion-exchangeable, layeredaluminosilicates such as pillared clays. Although the term “support” isused, it is not meant to be construed as an inert component of thecatalyst composition, but rather is to be considered an active part ofthe catalyst composition, because of its intimate association with themetallocene component.

According to another aspect of the present invention, the clay materialsof this invention encompass materials either in their natural state orthat have been treated with various ions by wetting, ion exchange, orpillaring. Typically, the clay material activator-support of thisinvention comprises clays that have been ion exchanged with largecations, including polynuclear, highly charged metal complex cations.However, the clay material activator-supports of this invention alsoencompass clays that have been ion exchanged with simple salts,including, but not limited to, salts of Al(III), Fe(II), Fe(III), andZn(II) with ligands such as halide, acetate, sulfate, nitrate, ornitrite.

According to another aspect of the present invention, the additionalactivator-support comprises a pillared clay. The term “pillared clay” isused to refer to clay materials that have been ion exchanged with large,typically polynuclear, highly charged metal complex cations. Examples ofsuch ions include, but are not limited to, Keggin ions which can havecharges such as 7+, various polyoxometallates, and other large ions.Thus, the term pillaring refers to a simple exchange reaction in whichthe exchangeable cations of a clay material are replaced with large,highly charged ions, such as Keggin ions. These polymeric cations arethen immobilized within the interlayers of the clay and when calcinedare converted to metal oxide “pillars,” effectively supporting the claylayers as column-like structures. Thus, once the clay is dried andcalcined to produce the supporting pillars between clay layers, theexpanded lattice structure is maintained and the porosity is enhanced.The resulting pores can vary in shape and size as a function of thepillaring material and the parent clay material used. Examples ofpillaring and pillared clays are found in: T. J. Pinnavaia, Science 220(4595), 365-371 (1983); J. M. Thomas, Intercalation Chemistry, (S.Whittington and A. Jacobson, eds.) Ch. 3, pp. 55-99, Academic Press,Inc., (1972); U.S. Pat. No. 4,452,910; U.S. Pat. No. 5,376,611; and U.S.Pat. No. 4,060,480; the disclosures of which are incorporated herein byreference in their entirety.

The pillaring process utilizes clay minerals having exchangeable cationsand layers capable of expanding. Any pillared clay that can enhance thepolymerization of olefins in the catalyst composition of the presentinvention can be used. Therefore, suitable clay minerals for pillaringinclude, but are not limited to, allophanes; smectites, bothdioctahedral (Al) and tri-octahedral (Mg) and derivatives thereof suchas montmorillonites (bentonites), nontronites, hectorites, or laponites;halloysites; vermiculites; micas; fluoromicas; chlorites; mixed-layerclays; the fibrous clays including but not limited to sepiolites,attapulgites, and palygorskites; a serpentine clay; illite; laponite;saponite; and any combination thereof. In one aspect, the pillared clayactivator-support comprises bentonite or montmorillonite. The principalcomponent of bentonite is montmorillonite.

The pillared clay can be pretreated if desired. For example, a pillaredbentonite is pretreated by drying at about 300° C. under an inertatmosphere, typically dry nitrogen, for about 3 hours, before beingadded to the polymerization reactor. Although an exemplary pretreatmentis described herein, it should be understood that the preheating can becarried out at many other temperatures and times, including anycombination of temperature and time steps, all of which are encompassedby this invention.

The activator-supports used to prepare the catalyst compositions of thepresent invention can be combined with other inorganic supportmaterials, including, but not limited to, zeolites, inorganic oxides,phosphated inorganic oxides, and the like. In one aspect, typicalsupport materials that are used include, but are not limited to, silica,silica-alumina, alumina, titania, zirconia, magnesia, boria, thoria,aluminophosphate, aluminum phosphate, silica-titania, co-precipitatedsilica/titania, mixtures thereof, or any combination thereof

Metallocene Compounds

The metal-containing sulfated activator-supports of the presentinvention can be employed in a catalyst composition with one or moremetallocene compounds. Generally, there is no limitation on theselection of the metallocene compound that can be used in combinationwith the metal-containing sulfated activator-supports of the presentinvention. Often, the transition metal in the metallocene compound isTi, Zr, or HE Some examples of suitable ansa-metallocene compoundsinclude, but are not limited to:

and the like. Applicants have used the abbreviations Ph for phenyl, Mefor methyl, and t-Bu for tert-butyl.

The following representative bridged metallocene compounds also can beemployed in catalyst compositions of the present invention:

and the like.

Additional examples of metallocene compounds that are suitable for usein catalyst compositions of the present invention are contemplated.These include, but are not limited to:

and the like.

The following non-limiting examples of two-carbon bridged metallocenecompounds also can be used in catalyst compositions of the presentinvention:

and the like. The integer n′ in these metallocene compounds generallyranges from 0 to about 10, inclusive. For example, n′ can be 1, 2, 3, 4,5, 6, 7, or 8.

Other bridged metallocene compounds can be employed in catalystcompositions of the present invention. Therefore, the scope of thepresent invention is not limited to the bridged metallocene speciesprovided above.

Likewise, unbridged metallocene compounds can be used in accordance withthe present invention. Such compounds include, but are not limited to:

and the like.

Additional suitable unbridged metallocene compounds include, but are notlimited to, the following compounds:

and the like.

Other unbridged metallocene compounds can be employed in catalystcompositions of the present invention. Therefore, the scope of thepresent invention is not limited to the unbridged metallocene speciesprovided above. Other metallocene compounds, including half-sandwich andcyclodienyl compounds, are suitable for use in catalyst compositions ofthe present invention, and such compounds include, but are not limitedto, the following:

and the like, wherein i-Pr is an abbreviation for isopropyl.Organoaluminum Compounds

In one aspect, catalyst compositions of the present invention cancomprise organoaluminum compounds. Such compounds include, but are notlimited to, compounds having the formula:(R¹)₃Al;where R¹ is an aliphatic group having from 2 to 10 carbon atoms. Forexample, R¹ can be ethyl, propyl, butyl, hexyl, or isobutyl.

Other organoaluminum compounds which can be used in catalystcompositions disclosed herein can include, but are not limited to,compounds having the formula:Al(X¹)_(m)(X²)_(3-m),where X¹ is a hydrocarbyl; X² is an alkoxide or an aryloxide, a halide,or a hydride; and m is from 1 to 3, inclusive. The term “hydrocarbyl” isused herein to specify a hydrocarbon radical group and includes, but isnot limited to, aryl, alkyl, cycloalkyl, alkenyl, cycloalkenyl,cycloalkadienyl, alkynyl, aralkyl, aralkenyl, aralkynyl, and the like,and includes all substituted, unsubstituted, branched, linear, orheteroatom substituted derivatives thereof

In one aspect, X¹ is a hydrocarbyl having from 1 to about 20 carbonatoms. In another aspect of the present invention, X¹ is an alkyl havingfrom 1 to 10 carbon atoms. For example, X¹ can be ethyl, propyl,n-butyl, sec-butyl, isobutyl, or hexyl, and the like, in yet anotheraspect of the present invention.

According to one aspect of the present invention, X² is an alkoxide oran aryloxide, any one of which has from 1 to 20 carbon atoms, a halide,or a hydride. In another aspect of the present invention, X² is selectedindependently from fluorine or chlorine. Yet, in another aspect, X² ischlorine.

In the formula, Al(X¹)_(m)(X²)_(3-m), m is a number from 1 to 3,inclusive, and typically, m is 3. The value of m is not restricted to bean integer; therefore, this formula includes sesquihalide compounds orother organoaluminum cluster compounds.

Examples of organoaluminum compounds suitable for use in accordance withthe present invention include, but are not limited to, trialkylaluminumcompounds, dialkylaluminum halide compounds, dialkylaluminum alkoxidecompounds, dialkylaluminum hydride compounds, and combinations thereof.Specific non-limiting examples of suitable organoaluminum compoundsinclude trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof.

The present invention contemplates a method of precontacting ametallocene compound with an organoaluminum compound and an olefinmonomer to form a precontacted mixture, prior to contacting thisprecontacted mixture with an activator-support to form a catalystcomposition. When the catalyst composition is prepared in this manner,typically, though not necessarily, a portion of the organoaluminumcompound is added to the precontacted mixture and another portion of theorganoaluminum compound is added to the postcontacted mixture preparedwhen the precontacted mixture is contacted with the solid oxideactivator-support. However, the entire organoaluminum compound can beused to prepare the catalyst composition in either the precontacting orpostcontacting step. Alternatively, all the catalyst components arecontacted in a single step.

Further, more than one organoaluminum compound can be used in either theprecontacting or the postcontacting step. When an organoaluminumcompound is added in multiple steps, the amounts of organoaluminumcompound disclosed herein include the total amount of organoaluminumcompound used in both the precontacted and postcontacted mixtures, andany additional organoaluminum compound added to the polymerizationreactor. Therefore, total amounts of organoaluminum compounds aredisclosed regardless of whether a single organoaluminum compound or morethan one organoaluminum compound is used.

Aluminoxane Compounds

The present invention further provides a catalyst composition which cancomprise an aluminoxane compound. As used herein, the term “aluminoxane”refers to aluminoxane compounds, compositions, mixtures, or discretespecies, regardless of how such aluminoxanes are prepared, formed orotherwise provided. For example, a catalyst composition comprising analuminoxane compound can be prepared in which aluminoxane is provided asthe poly(hydrocarbyl aluminum oxide), or in which aluminoxane isprovided as the combination of an aluminum alkyl compound and a sourceof active protons such as water. Aluminoxanes are also referred to aspoly(hydrocarbyl aluminum oxides) or organoaluminoxanes.

The other catalyst components typically are contacted with thealuminoxane in a saturated hydrocarbon compound solvent, though anysolvent that is substantially inert to the reactants, intermediates, andproducts of the activation step can be used. The catalyst compositionformed in this manner is collected by any suitable method, for example,by filtration. Alternatively, the catalyst composition is introducedinto the polymerization reactor without being isolated.

The aluminoxane compound of this invention can be an oligomeric aluminumcompound comprising linear structures, cyclic structures, or cagestructures, or mixtures of all three. Cyclic aluminoxane compoundshaving the formula:

wherein R is a linear or branched alkyl having from 1 to 10 carbonatoms, and p is an integer from 3 to 20, are encompassed by thisinvention. The ARO moiety shown here also constitutes the repeating unitin a linear aluminoxane. Thus, linear aluminoxanes having the formula:

wherein R is a linear or branched alkyl having from 1 to 10 carbonatoms, and q is an integer from 1 to 50, are also encompassed by thisinvention.

Further, aluminoxanes can have cage structures of the formula R^(t)_(5r+α)R^(b) _(r−α)Al_(4r)O_(3r), wherein R^(t) is a terminal linear orbranched alkyl group having from 1 to 10 carbon atoms; R^(b) is abridging linear or branched alkyl group having from 1 to 10 carbonatoms; r is 3 or 4; and a is equal to n_(Al(3))-n_(O(2))+n_(O(4)),wherein n_(Al(3)) is the number of three coordinate aluminum atoms,n_(O(2)) is the number of two coordinate oxygen atoms, and n_(O(4)) isthe number of 4 coordinate oxygen atoms.

Thus, aluminoxanes which can be employed in the catalyst compositions ofthe present invention are represented generally by formulas such as(R—Al—O)_(p), R(R—Al—O)_(q)AlR₂, and the like. In these formulas, the Rgroup is typically a linear or branched C₁-C₆ alkyl, such as methyl,ethyl, propyl, butyl, pentyl, or hexyl. Examples of aluminoxanecompounds that can be used in accordance with the present inventioninclude, but are not limited to, methylaluminoxane, ethylaluminoxane,n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane,t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,isopentylaluminoxane, neopentylaluminoxane, and the like, or anycombination thereof. Methylaluminoxane, ethylaluminoxane, andiso-butylaluminoxane are prepared from trimethylaluminum,triethylaluminum, or triisobutylaluminum, respectively, and sometimesare referred to as poly(methyl aluminum oxide), poly(ethyl aluminumoxide), and poly(isobutyl aluminum oxide), respectively. It is alsowithin the scope of the invention to use an aluminoxane in combinationwith a trialkylaluminum, such as that disclosed in U.S. Pat. No.4,794,096, incorporated herein by reference in its entirety.

The present invention contemplates many values of p and q in thealuminoxane formulas (R—Al—O)_(p) and R(R—Al—O)_(q)AlR₂, respectively.In some aspects, p and q are at least 3. However, depending upon how theorganoaluminoxane is prepared, stored, and used, the value of p and qcan vary within a single sample of aluminoxane, and such combinations oforganoaluminoxanes are contemplated herein.

In preparing a catalyst composition containing an aluminoxane, the molarratio of the total moles of aluminum in the aluminoxane (oraluminoxanes) to the total moles of metallocene compound (or compounds)in the composition is generally between about 1:10 and about 100,000:1.In another aspect, the molar ratio is in a range from about 5:1 to about15,000:1. Optionally, aluminoxane can be added to a polymerization zonein ranges from about 0.01 mg/L to about 1000 mg/L, from about 0.1 mg/Lto about 100 mg/L, or from about 1 mg/L to about 50 mg/L.

Organoaluminoxanes can be prepared by various procedures. Examples oforganoaluminoxane preparations are disclosed in U.S. Pat. Nos. 3,242,099and 4,808,561, the disclosures of which are incorporated herein byreference in their entirety. For example, water in an inert organicsolvent can be reacted with an aluminum alkyl compound, such as (R¹)₃Al,to form the desired organoaluminoxane compound. While not intending tobe bound by this statement, it is believed that this synthetic methodcan afford a mixture of both linear and cyclic R—Al—O aluminoxanespecies, both of which are encompassed by this invention. Alternatively,organoaluminoxanes can be prepared by reacting an aluminum alkylcompound, such as (R¹)₃Al with a hydrated salt, such as hydrated coppersulfate, in an inert organic solvent.

Organoboron/Organoborate Compounds

According to another aspect of the present invention, the catalystcomposition can comprise an organoboron or organoborate activator.Organoboron or organoborate compounds include neutral boron compounds,borate salts, and the like, or combinations thereof. For example,fluoroorgano boron compounds and fluoroorgano borate compounds arecontemplated.

Any fluoroorgano boron or fluoroorgano borate compound can be utilizedwith the present invention. Examples of fluoroorgano borate compoundsthat can be used in the present invention include, but are not limitedto, fluorinated aryl borates such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like, ormixtures thereof. Examples of fluoroorgano boron compounds that can beused in the present invention include, but are not limited to,tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,and the like, or mixtures thereof. Although not intending to be bound bythe following theory, these examples of fluoroorgano borate andfluoroorgano boron compounds, and related compounds, are thought to form“weakly-coordinating” anions when combined with organometal ormetallocene compounds, as disclosed in U.S. Pat. No. 5,919,983, thedisclosure of which is incorporated herein by reference in its entirety.Applicants also contemplate the use of diboron, or bis-boron, compoundsor other bifunctional compounds containing two or more boron atoms inthe chemical structure, such as disclosed in J. Am. Chem. Soc., 2005,127, pp. 14756-14768, the content of which is incorporated herein byreference in its entirety.

Generally, any amount of organoboron compound can be used. According toone aspect of this invention, the molar ratio of the total moles oforganoboron or organoborate compound (or compounds) to the total molesof metallocene compound (or compounds) in the catalyst composition is ina range from about 0.1:1 to about 15:1. Typically, the amount of thefluoroorgano boron or fluoroorgano borate compound used is from about0.5 moles to about 10 moles of boron/borate compound per mole ofmetallocene compound. According to another aspect of this invention, theamount of fluoroorgano boron or fluoroorgano borate compound is fromabout 0.8 moles to about 5 moles of boron/borate compound per mole ofmetallocene compound.

Ionizing Ionic Compounds

The present invention further provides a catalyst composition which cancomprise an ionizing ionic compound. An ionizing ionic compound is anionic compound that can function as an activator or co-catalyst toenhance the activity of the catalyst composition. While not intending tobe bound by theory, it is believed that the ionizing ionic compound iscapable of reacting with a metallocene compound and converting themetallocene into one or more cationic metallocene compounds, orincipient cationic metallocene compounds. Again, while not intending tobe bound by theory, it is believed that the ionizing ionic compound canfunction as an ionizing compound by completely or partially extractingan anionic ligand, possibly a non-alkadienyl ligand from themetallocene. However, the ionizing ionic compound is an activatorregardless of whether it ionizes the metallocene, abstracts a ligand ina fashion as to form an ion pair, weakens the metal-ligand bond in themetallocene, simply coordinates to a ligand, or activates themetallocene compound by some other mechanism.

Further, it is not necessary that the ionizing ionic compound activatethe metallocene compound(s) only. The activation function of theionizing ionic compound can be evident in the enhanced activity ofcatalyst composition as a whole, as compared to a catalyst compositionthat does not contain an ionizing ionic compound.

Examples of ionizing ionic compounds include, but are not limited to,the following compounds: tri(n-butyl)ammonium tetrakis(p-tolyl)borate,tri(n-butyl) ammonium tetrakis(m-tolyl)borate, tri(n-butyl)ammoniumtetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(p-tolyl)borate, N,N-dimethylanilinium tetrakis(m-tolyl)borate,N,N-dimethylanilinium tetrakis(2,4-dimethylphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-dimethyl-phenyl)borate,N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,N,N-dimethylanilinium tetrakis(pentafluorophenyeborate,triphenylcarbenium tetrakis(p-tolyl)borate, triphenylcarbeniumtetrakis(m-tolyl)borate, triphenylcarbeniumtetrakis(2,4-dimethylphenyl)borate, triphenylcarbeniumtetrakis(3,5-dimethylphenyl)borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, tropylium tetrakis(p-tolyl)borate,tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis-(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyealuminate, sodium tetraphenylaluminate,sodium tetrakis(p-tolyl)aluminate, sodium tetrakis(m-tolyl)aluminate,sodium tetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyealuminate, potassiumtetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,and the like, or combinations thereof. Ionizing ionic compounds usefulin this invention are not limited to these; other examples of ionizingionic compounds are disclosed in U.S. Pat. Nos. 5,576,259 and 5,807,938,the disclosures of which are incorporated herein by reference in theirentirety.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically include olefincompounds having from about 2 to 30 carbon atoms per molecule and havingat least one olefinic double bond.

This invention encompasses homopolymerization processes using a singleolefin such as ethylene or propylene, as well as copolymerization,terpolymerization, etc., reactions with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally contain a major amount of ethylene (>50 mole percent)and a minor amount of comonomer (<50 mole percent), though this is not arequirement. Comonomers that can be copolymerized with ethylene oftenhave from 3 to 20 carbon atoms in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes, the four normal nonenes, the five normaldecenes, and the like, or mixtures of two or more of these compounds.Cyclic and bicyclic olefins, including but not limited to, cyclopentene,cyclohexene, norbornylene, norbornadiene, and the like, also can bepolymerized as described above. Styrene can also be employed as amonomer in the present invention.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer can comprise, for example, ethylene or propylene, which iscopolymerized with at least one comonomer. According to one aspect ofthis invention, the olefin monomer in the polymerization process isethylene. In this aspect, examples of suitable olefin comonomersinclude, but are not limited to, propylene, 2-methylpropene, 1-butene,2-butene, 3-methyl-1-butene, 1-pentene, 2-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene,2-heptene, 3-heptene, 1-octene, 1-decene, styrene, and the like, orcombinations thereof. According to one aspect of the present invention,the comonomer is 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, orstyrene, or any combination thereof.

Generally, the amount of comonomer introduced into a reactor zone toproduce the copolymer is from about 0.01 to about 50 weight percent ofthe comonomer based on the total weight of the monomer and comonomer.According to another aspect of the present invention, the amount ofcomonomer introduced into a reactor zone is from about 0.01 to about 40weight percent comonomer based on the total weight of the monomer andcomonomer. In still another aspect, the amount of comonomer introducedinto a reactor zone is from about 0.1 to about 35 weight percentcomonomer based on the total weight of the monomer and comonomer. Yet,in another aspect, the amount of comonomer introduced into a reactorzone is from about 0.5 to about 20 weight percent comonomer based on thetotal weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight. According to one aspect of the present invention, onemonomer/reactant is ethylene, so the polymerizations are either ahomopolymerization involving only ethylene, or copolymerizations with adifferent acyclic, cyclic, terminal, internal, linear, branched,substituted, or unsubstituted olefin. In addition, the catalystcompositions and processes of this invention can be used in thepolymerization of diolefin compounds including, but not limited to,1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Polymerization Process

Catalyst compositions of the present invention can be used to polymerizeolefins to form copolymers, terpolymers, and the like. One such processfor polymerizing olefins in the presence of a catalyst compositioncomprises contacting the catalyst composition with an olefin monomer andoptionally an olefin comonomer under polymerization conditions toproduce an olefin polymer, wherein the catalyst composition comprises acontact product of a metallocene compound and a metal-containingsulfated activator-support. The metal-containing sulfatedactivator-support comprises a contact product of (i) a transition metalcompound; (ii) a sulfate compound; and (iii) a solid oxide.

Often, a catalyst composition of the present invention, employed in apolymerization process, will further comprise at least oneorganoaluminum compound. Suitable organoaluminum compounds include, butare not limited to, trimethylaluminum, triethylaluminum,tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, and the like, or anycombination thereof.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactors. As used herein, “polymerization reactor” includes anypolymerization reactor capable of polymerizing olefin monomers andcomonomers (one or more than one comonomer) to produce homopolymers,copolymers, terpolymers, and the like. The various types of reactorsinclude those that may be referred to as batch, slurry, gas phase,solution, high pressure, tubular, or autoclave reactors. Gas phasereactors may comprise fluidized bed reactors or staged horizontalreactors. Slurry reactors may comprise vertical or horizontal loops.High pressure reactors may comprise autoclave or tubular reactors.Reactor types can include batch or continuous processes. Continuousprocesses could use intermittent or continuous product discharge.Processes may also include partial or full direct recycle of unreactedmonomer, unreacted comonomer, and/or diluent.

Polymerization reactor systems of the present invention may comprise onetype of reactor in a system or multiple reactors of the same ordifferent type. Production of polymers in multiple reactors may includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorsmay be different from the operating conditions of the other reactors.Alternatively, polymerization in multiple reactors may include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems may include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors maybe operated in series or in parallel.

According to one aspect of the invention, the polymerization reactorsystem may comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and optionally anycomonomer may be continuously fed to a loop reactor where polymerizationoccurs. Generally, continuous processes may comprise the continuousintroduction of monomer/comonomer, a catalyst, and a diluent into apolymerization reactor and the continuous removal from this reactor of asuspension comprising polymer particles and the diluent. Reactoreffluent may be flashed to remove the solid polymer from the liquidsthat comprise the diluent, monomer and/or comonomer. Varioustechnologies may be used for this separation step including but notlimited to, flashing that may include any combination of heat additionand pressure reduction; separation by cyclonic action in either acyclone or hydrocyclone; or separation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under reaction conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. No. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another aspect of this invention, the polymerizationreactor may comprise at least one gas phase reactor. Such systems mayemploy a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream may bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product may be withdrawn from the reactor andnew or fresh monomer may be added to replace the polymerized monomer.Such gas phase reactors may comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect of the invention, a high pressurepolymerization reactor may comprise a tubular reactor or an autoclavereactor. Tubular reactors may have several zones where fresh monomer,initiators, or catalysts are added. Monomer may be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components may be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamsmay be intermixed for polymerization. Heat and pressure may be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor may comprise a solution polymerization reactor wherein themonomer/comonomer are contacted with the catalyst composition bysuitable stirring or other means. A carrier comprising an inert organicdiluent or excess monomer may be employed. If desired, themonomer/comonomer may be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation may be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactors suitable for the present invention may furthercomprise any combination of at least one raw material feed system, atleast one feed system for catalyst or catalyst components, and/or atleast one polymer recovery system. Suitable reactor systems for thepresent invention may further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Conditions that are controlled for polymerization efficiency and toprovide desired polymer properties include temperature, pressure, andthe concentrations of various reactants. Polymerization temperature canaffect catalyst productivity, polymer molecular weight, and molecularweight distribution. Suitable polymerization temperature may be anytemperature below the de-polymerization temperature according to theGibbs Free energy equation. Typically, this includes from about 60° C.to about 280° C., for example, or from about 60° C. to about 110° C.,depending upon the type of polymerization reactor. In some reactorsystems, the polymerization temperature generally is within a range fromabout 70° C. to about 90° C., or from about 75° C. to about 85° C.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig. Pressure for gas phasepolymerization is usually at about 200 to 500 psig. High pressurepolymerization in tubular or autoclave reactors is generally run atabout 20,000 to 75,000 psig. Polymerization reactors can also beoperated in a supercritical region occurring at generally highertemperatures and pressures. Operation above the critical point of apressure/temperature diagram (supercritical phase) may offer advantages.

According to one aspect of this invention, the feed ratio of hydrogen tothe olefin monomer in the polymerization process is controlled. Thisweight ratio can range from about 0 ppm to about 10,000 ppm of hydrogen,based on the weight of the olefin monomer. For instance, the reactant orfeed ratio of hydrogen to olefin monomer can be controlled at a weightratio which falls within a range from about 50 ppm to about 7500 ppm,from about 50 ppm to about 5000 ppm, or from about 50 ppm to about 1000ppm.

In ethylene polymerizations, the feed ratio of hydrogen to ethylenemonomer, irrespective of comonomer(s) employed, generally is controlledat a weight ratio within a range from about 0 ppm to about 1000 ppm, butthe specific weight ratio target can depend upon the desired polymermolecular weight or melt index (MI). For ethylene polymers (copolymers,terpolymers, etc.) having a MI around 1 g/10 min, the weight ratio ofhydrogen to ethylene is typically in a range from about 50 ppm to about250 ppm, such as, for example, from about 75 ppm to about 225 ppm, orfrom about 100 ppm to about 200 ppm.

Yet, in another aspect, effluent flush gas from the polymerizationreactors disclosed herein generally has a hydrogen to olefin monomermolar ratio of less than about 0.01, although this ratio can depend uponthe desired polymer molecular weight, melt index, etc. In an ethylenepolymerization, the hydrogen:ethylene molar ratio is typically less thanabout 0.01, and often, less than about 0.005.

The polymerization process disclosed herein can be conducted in a singlereactor in certain aspects of this invention. Thus, multiple reactorsystems are not required. An olefin polymer (e.g., an ethylenecopolymer) can be produced in the presence of hydrogen and ametallocene-based catalyst system, in a single reactor, resulting in apolymer with a ratio of Mz/Mw greater than about 3. Further, the singlereactor can be, as discussed above, a gas phase reactor, a loop reactor,or a stirred tank reactor, for example.

The concentration of the reactants entering the polymerization reactorcan be controlled to produce resins with certain physical and mechanicalproperties. The proposed end-use product that will be formed by thepolymer resin and the method of forming that product ultimately candetermine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to the polymers produced by any of thepolymerization processes disclosed herein. Articles of manufacture canbe formed from, and can comprise, the polymers produced in accordancewith this invention.

Polymers and Articles

If the resultant polymer produced in accordance with the presentinvention is, for example, a polymer or copolymer of ethylene, itsproperties can be characterized by various analytical techniques knownand used in the polyolefin industry. Articles of manufacture can beformed from, and can comprise, the ethylene polymers of this invention,whose typical properties are provided below.

Polymers of ethylene (copolymers, terpolymers, etc.) produced inaccordance with this invention generally have a melt index from about0.001 to about 10 g/10 min. Melt indices in the range from about 0.001to about 5 g/10 min, or from about 0.01 to about 3 g/10 min, arecontemplated in some aspects of this invention. For example, a polymerof the present invention can have a melt index in a range from about0.05 to about 3, from about 0.1 to about 2, or from about 0.5 to about1.5 g/10 min.

The density of ethylene-based polymers produced using a metal-containingsulfated activator-support disclosed herein typically falls within therange from about 0.88 to about 0.97 g/cm³. In one aspect of thisinvention, the density of an ethylene polymer is in a range from about0.90 to about 0.94 g/cm³. Yet, in another aspect, the density is in arange from about 0.91 to about 0.93 g/cm³, such as, for example, fromabout 0.915 to about 0.925 g/cm³.

Ethylene polymers, such as copolymers and terpolymers, within the scopeof the present invention generally have a number-average molecularweight (Mn) in a range from about 60,000 to about 350,000 g/mol, aweight-average molecular weight (Mw) in a range from about 100,000 toabout 2,000,000 g/mol, and a z-average molecular weight (Mz) in a rangefrom about 1,000,000 to about 5,000,000 g/mol. The ratio of Mz/Mw forthe polymers of this invention often are greater than about 3, such as,for example, greater than about 3.5, or greater than about 4. In someaspects, the ratio of Mz/Mw falls within a range from about 3 to about5.

The molecular weight distribution can be considered to consist of twocomponents, one being a typical unimodal, bell-shaped curve, and theother being the high molecular weight tail, generally believed to resultfrom the metal-containing sulfated activator-support. Based on the totalweight of polymer, the weight fraction of the high molecular weight tailcan fall within a range from about 1 to about 25 percent, or from about1 to about 15 percent. In some aspects of this invention, the weightfraction of polymer in the high molecular weight tail is in a range fromabout 1 to about 10 percent. The Mw of the high molecular weight tailcan be a high as 2,500,000 g/mol, or more. For instance, the Mw of thehigh molecular weight tail can be greater than about 3,000,000, orgreater than about 3,500,000 g/mol.

By far the largest weight fraction of the polymer is encompassed by thetypical bell-shaped molecular weight distribution curve. One measure ofthe breadth of the molecular weight distribution of this portion of thepolymer is the polydispersity index, or the ratio of Mw/Mn. Generally,the ratios of Mw/Mn for this fraction of the polymer are in a range fromabout 2 to about 6. In some aspects, this Mw/Mn ratio is in a range fromabout 2 to about 4, or from about 2 to about 3. The peak molecularweight for this fraction of the polymer is generally less than about500,000 g/mol, for example, less than about 400,000 g/mol, less thanabout 200,000 g/mol, or less than about 100,000 g/mol. It is alsobelieved that the Carreau-Yasuda breadth parameter (CY-a) for thisportion of the polymer is greater than about 0.3, greater than about0.4, or greater than about 0.5. Details on the significance andinterpretation of the Carreau-Yasuda empirical model may be found in: C.A. Hieber and H. H. Chiang, Rheol. Acta, 28, 321 (1989); C. A. Hieberand H. H. Chiang, Polym. Eng. Sci., 32, 931 (1992); and R. B. Bird, R.C. Armstrong and O. Hasseger, Dynamics of Polymeric Liquids, Volume 1,Fluid Mechanics, 2nd Edition, John Wiley & Sons (1987); each of which isincorporated herein by reference in its entirety.

Due to the high molecular weight tail, it is contemplated that theincrease in the ratio of Mz/Mw due to the presence of the high molecularweight tail, as compared to a standard bell-shaped profile, is greaterthan about 50%. For instance, the ratio of Mz/Mw can be increased byabout 75% or more, or by about 100% or more, due to the incorporation ofa metal-containing sulfated activator-support in the catalyst system.The high molecular weight tail also can have much less long chainbranching than the portion of the polymer represented by the traditionalbell-shaped curve. Often, the amount of long chain branching in the highmolecular weight tail is less than ½, or less than ⅓, or less than ¼, ofthat found in the other portion of the polymer.

In the overall molecular weight distribution of the polymer, the weightpercent of the total polymer having a molecular weight greater than3,000,000 g/mol is generally from about 0.5 to about 20 percent, or fromabout 1 to about 15 percent. That is, the weight percent of the polymerhaving a molecular weight greater than 3,000,000 g/mol can be in a rangefrom about 2 to about 10 percent, or from about 3 to about 8 percent.Additionally, the weight percent of the total polymer having a molecularweight greater than 1,000,000 g/mol can be from about 4.5 to about 50percent. In some aspects, the weight percent of the polymer having amolecular weight greater than 1,000,000 g/mol is in a range from about4.5 to about 35 percent, from about 4.5 to about 30 percent, from about5 to about 25 percent, or from about 6 to about 20 percent.

Polymers of ethylene, whether copolymers, terpolymers, and so forth, canbe formed into various articles of manufacture. Articles which cancomprise polymers of this invention include, but are not limited to, anagricultural film, an automobile part, a bottle, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, a toy,and the like. Various processes can be employed to form these articles.Non-limiting examples of these processes include injection molding, blowmolding, rotational molding, film extrusion, sheet extrusion, profileextrusion, thermoforming, and the like. Additionally, additives andmodifiers are often added to these polymers in order to providebeneficial polymer processing or end-use product attributes.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

Molecular weights and molecular weight distributions were obtained usinga PL 220 SEC high temperature chromatography unit (Polymer Laboratories)with trichlorobenzene (TCB) as the solvent, with a flow rate of 1mL/minute at a temperature of 145° C. BHT(2,6-di-tert-butyl-4-methylphenol) at a concentration of 0.5 g/L wasused as a stabilizer in the TCB. An injection volume of 200 uL was usedwith a nominal polymer concentration of 1.5 mg/mL. Dissolution of thesample in stabilized TCB was carried out by heating at 150° C. for 5hours with occasional, gentle agitation. The columns used were threePLgel Mixed A LS columns (7.8×300 mm) and were calibrated with a broadlinear polyethylene standard (Phillips Marlex® BHB 5003) for which themolecular weight had been determined.

Ethylene was polymerization grade ethylene obtained from Air GasSpecialty Gases. This ethylene was then further purified through acolumn of ¼-inch beads of Alcoa A201 alumina, activated at about 250° C.in nitrogen. Isobutane was polymerization grade obtained from EnterpriseProducts, which was further purified by distillation and then alsopassed through a column of ¼-inch beads of Alcoa A201 alumina, activatedat about 250° C. in nitrogen. Triisobutylaluminum (TIBA) was obtainedfrom Akzo Corporation as a one molar solution in heptane.

The fluorided silica-alumina employed in Examples 6 and 14 was preparedin accordance with the following procedure. A silica-alumina wasobtained from W.R. Grace Company containing about 13% alumina by weightand having a surface area of about 400 m²/g and a pore volume of about1.2 mL/g. This material was obtained as a powder having an averageparticle size of about 70 microns. Approximately 100 grams of thismaterial were impregnated with a solution containing about 200 mL ofwater and about 10 grams of ammonium hydrogen fluoride, resulting in adamp powder having the consistency of wet sand. This mixture was thenplaced in a flat pan and allowed to dry under vacuum at approximately110° C. for about 16 hours.

To calcine the support, about 10 grams of this powdered mixture wereplaced in a 1.75-inch quartz tube fitted with a sintered quartz disk atthe bottom. While the powder was supported on the disk, air (nitrogencan be substituted) dried by passing through a 13× molecular sievecolumn, was blown upward through the disk at the linear rate of about1.6 to 1.8 standard cubic feet per hour. An electric furnace around thequartz tube was then turned on and the temperature was raised at therate of about 400° C. per hour to the desired calcining temperature ofabout 450° C. At this temperature, the powder was allowed to fluidizefor about three hours in the dry air. Afterward, the fluoridedsilica-alumina was collected and stored under dry nitrogen, and was usedwithout exposure to the atmosphere.

The sulfated alumina activator-support employed in Examples 1-4, 7-12,and 15-16 was prepared in accordance with the following procedure.Bohemite was obtained from W.R. Grace Company under the designation“Alumina A” and having a surface area of about 300 m²/g and a porevolume of about 1.3 mL/g. This material was obtained as a powder havingan average particle size of about 100 microns. This material wasimpregnated to incipient wetness with an aqueous solution of ammoniumsulfate to equal about 15% sulfate. This mixture was then placed in aflat pan and allowed to dry under vacuum at approximately 110° C. forabout 16 hours.

To calcine the support, about 10 grams of this powdered mixture wereplaced in a 1.75-inch quartz tube fitted with a sintered quartz disk atthe bottom. While the powder was supported on the disk, air (nitrogencan be substituted) dried by passing through a 13× molecular sievecolumn, was blown upward through the disk at the linear rate of about1.6 to 1.8 standard cubic feet per hour. An electric furnace around thequartz tube was then turned on and the temperature was raised at therate of about 400° C. per hour to the desired calcining temperature ofabout 600° C. At this temperature, the powder was allowed to fluidizefor about three hours in the dry air. Afterward, the sulfated aluminaactivator-support was collected and stored under dry nitrogen, and wasused without exposure to the atmosphere.

The chlorided zinc aluminate activator-support employed in Examples 5and 13 was prepared in accordance with the following procedure. Amixture of 100 mL of deionized water, 13.03 grams of zinc chloride, anda few drops of nitric acid was made and contacted with 64.84 grams ofKetjen Grade B alumina. Zinc chloride is not a transition metal compoundof this invention. The zinc chloride loading was 20% of the aluminaAfter drying overnight under vacuum at 100° C. and pushing through a 100mesh screen, a portion of this material was calcined in dry air at 600°C. for three hours to produce the zinc aluminate mixed oxide.Approximately 35.9 g of the zinc aluminate were heated under nitrogen to600° C. and, while maintaining this temperature, 5.5 mL of carbontetrachloride were added to chloridate the zinc aluminate. Afterward,the chlorided zinc aluminate activator-support was collected and storedunder nitrogen, and was used without exposure to the atmosphere.

All polymerizations were carried out in a one-gallon stirred reactoraccording to the following general procedure. First, the reactor waspurged with nitrogen and heated to about 120° C. After cooling to belowabout 40° C. and purging with isobutane vapor, alkyl aluminum,activator-support, and the metallocene solution were added in that orderthrough a charge port while venting isobutane vapor. The reactor wasthen closed. The metallocene quantity varied from 0.2 to 2.0 mg. About0.5 mL of 1M triisobutylaluminum (TIBA) co-catalyst were used in eachpolymerization. Either 100 mg or 200 mg of the activator-support wereused in the polymerization. About 1.8 liters of isobutane were addedunder pressure, and the reactor was subsequently heated to either 90° C.or 95° C. The reactor contents were mixed at 900 rpm. Ethylene was thenadded to the reactor, along with hydrogen, if used, at a fixed massratio with respect to the ethylene flow. Hydrogen was stored in a 340-mLpressure vessel and added with the ethylene via an automated feedingsystem, while the reactor pressure was maintained at either 390 psig or420 psig by the combined ethylene/isobutane, or combinedhydrogen/ethylene/isobutane, addition. The reactor was maintained andcontrolled at either 90° C. or 95° C. throughout the 30-minute or60-minute run time of the polymerization. Upon completion, the isobutaneand ethylene were vented from the reactor, the reactor was opened, andthe polymer product was collected and dried.

Examples 1-8 Polymers Produced Using Titanium-Containing SulfatedAlumina

Approximately 2 mg were used in Examples 1-6, and 1 mg was used inExamples 7-8, of the following metallocene compound:

This compound can be prepared in accordance with any suitable method.One such technique is described in U.S. Pat. No. 7,064,225, thedisclosure of which is incorporated herein by reference in its entirety.

Certain polymerization components and the resultant polymer propertiesfor Examples 1-8 are listed in Table I. Examples 1, 3, and 7 wereComparative Examples using a sulfated alumina activator support, whileComparative Examples 5 and 6 employed titanium-containing chloridedalumina and titanium-containing fluorided silica-alumina, respectively.Examples 2, 4, and 8 utilized the titanium-containing sulfated aluminain accordance with this invention.

For Examples 2, 4-6, and 8, titanium was impregnated into the treatedsolid oxides by the following procedure. At room temperature (about 25°C.), TiCl₄ was dissolved in heptane and was added to a slurry of therespective treated solid oxide in heptane. TiCl₄ was used at a weightpercentage of about 1.1%, based on the weight of the treated solidoxide. This mixture was stirred for about 2 to 3 minutes. The solventwas removed under vacuum at a temperature of about 25 to 30° C.,resulting in a free-flowing solid, titanium-containingactivator-support. No subsequent calcining was conducted on thesetitanium-containing activator-supports.

Following the general polymerization procedure provided above, 100 mg ofthe activator-support were used for Examples 1-8, and the polymerizationprocess was conducted at a reactor temperature of 90° C., a reactorpressure of 390 psig, and a reaction time of 30 minutes.

FIG. 1 compares the molecular weight distributions of the polymers ofExamples 1 and 2, while FIG. 2 compares the molecular weightdistributions of Examples 3 and 4. As shown in Table I and FIGS. 1-2,polymers produced using the sulfated alumina activator-supportcontaining titanium had broader molecular weight distributions (e.g.,higher Mw/Mn and Mz/Mw) than the polymers produced using sulfatedalumina, whether in the presence or the absence of hydrogen. Highermolecular weight polymer was also produced due to the presence oftitanium in the activator-support, as reflected in the Mw and Mz valuesin Table I and the high molecular weight tail illustrated graphically inFIGS. 1-2.

As compared to the polymers of Examples 5-6, the polymer of Example 2,produced using a titanium-impregnated sulfated alumina activatorsupport, had a higher Mw and Mz, and a higher molecular weight tail asreflected in the ratio of Mz/Mw. Interestingly, the catalyst activity ofthe titanium-containing sulfated alumina was far superior to that ofeither titanium-containing chlorided zinc aluminate or fluoridedsilica-alumina, each evaluated under the same polymerization conditionsand using the same metallocene compound. The catalyst activity of thetitanium-containing sulfated alumina (Example 2) was 3.5 times that ofthe titanium-containing chlorided zinc aluminate (Example 5) and over 10times that of titanium-containing fluorided silica-alumina (Example 6).

In contrast with Examples 1-6, Examples 7-8 utilized only 1 mg of themetallocene compound depicted above. However, the same general resultswere found in Table I: polymers produced using the sulfated aluminaactivator-support containing titanium had broader molecular weightdistributions (e.g., higher Mw/Mn and Mz/Mw) and higher molecularweights (e.g., Mw, Mz) than the polymers produced using sulfated aluminawhich was not impregnated with titanium.

The weight percent of the total polymer of Example 2, Example 4, andExample 8 having a molecular weight greater than 1,000,000 g/mol was14.5%, 9.7%, and 18.4%, respectively. Additionally, the weight percentof the total polymer of Example 2, Example 4, and Example 8 having amolecular weight greater than 3,000,000 g/mol was 3.2%, 1.9%, and 7.3%,respectively.

TABLE I Polymerization Conditions and Polymer Properties of Examples1-8. H₂/Ethylene Activator- g PE Example Type Feed (ppm) Supportproduced 1 Comparative   0 SA 136 2 Inventive   0 SA-Ti 150 3Comparative 200 SA 182 4 Inventive 200 SA-Ti 150 5 Comparative   0CZA-Ti  42 6 Comparative   0 FSA-Ti  13 7 Comparative 200 SA  82 8Inventive 200 SA-Ti 111 Mn/1000 Mw/1000 Mz/1000 Mw/ Mz/ Example (g/mol)(g/mol) (g/mol) Mn Mw 1 182 383  710 2.1 1.9 2 231 656 2287 2.8 3.5 3 74 236  561 3.2 2.4 4 103 457 1797 4.5 3.9 5 177 493 1399 2.8 2.8 6 207506 1282 2.4 2.5 7  80 259  577 3.3 2.2 8  91 848 3978 9.3 4.7

Examples 9-10 Polymers Produced Using Vanadium-Containing SulfatedAlumina

In Examples 9-10, 2 mg of the metallocene compound used in Examples 1-8were employed, illustrated by the following structure:

Certain polymerization components and the resultant polymer propertiesfor Examples 9-10 are listed in Table II. Example 10 was a ComparativeExample using a sulfated alumina activator-support, while Example 9utilized a vanadium-containing sulfated alumina in accordance with thisinvention.

For Example 9, vanadium was impregnated into the sulfated alumina by thefollowing procedure. At room temperature (about 25° C.), VOCl₃ wasdissolved in heptane and was added to a slurry of the sulfated aluminain heptane. VOCl₃ was used at a weight percentage of about 1%, based onthe weight of the sulfated alumina. This mixture was stirred for about 2to 3 minutes. The solvent was removed under vacuum at a temperature ofabout 25 to 30° C., resulting in a free-flowing solid,vanadium-containing sulfated alumina No subsequent calcining wasconducted on the vanadium-containing sulfated alumina.

Following the general polymerization procedure provided above, 100 mg ofthe activator-support were used for Examples 9-10, and thepolymerization process was conducted at a reactor temperature of 90° C.,a reactor pressure of 390 psig, and a reaction time of 30 minutes.

FIG. 3 compares the molecular weight distributions of the polymers ofExamples 9 and 10. As shown in Table II and FIG. 3, a polymer producedusing the sulfated alumina activator-support containing vanadium hadbroader molecular weight distributions (e.g., higher Mw/Mn and Mz/Mw)than the polymer produced using sulfated alumina alone. Higher molecularweight polymer was also produced due to the presence of vanadium in theactivator-support, as reflected in the Mw and Mz values in Table II andthe high molecular weight tail illustrated graphically in FIG. 3. Theweight percent of the total polymer of Example 9 having a molecularweight greater than 1,000,000 g/mol was 6.2%, and greater than 3,000,000g/mol was 1.3%.

TABLE II Polymerization Conditions and Polymer Properties of Examples9-10. H₂/Ethylene Activator- g PE Example Type Feed (ppm) Supportproduced  9 Inventive 200 SA-V 178 10 Comparative 200 SA 189 Mn/1000Mw/1000 Mz/1000 Mw/ Mz/ Example (g/mol) (g/mol) (g/mol) Mn Mw  9 77 3591699 4.7 4.7 10 54 206  548 3.8 2.7

Examples 11-16 Polymers Produced Using Zirconium-Containing SulfatedAlumina

In Examples 11-14, the following metallocene compound was employed:

This compound can be prepared in accordance with any suitable method.One such technique is described in U.S. Patent Publication No.2007/0179044, the disclosure of which is incorporated herein byreference in its entirety.

Certain polymerization components and the resultant polymer propertiesfor Examples 11-16 are listed in Table III. Examples 12 and 15 wereComparative Examples using a sulfated alumina activator support, whileComparative Examples 13 and 14 employed zirconium-containing chloridedzinc aluminate and zirconium-containing fluorided silica-alumina,respectively. Examples 11 and 16 utilized the zirconium-containingsulfated alumina in accordance with this invention.

For Examples 11, 13-14, and 16, zirconium was impregnated into thetreated solid oxides by the following procedure. At room temperature(about 25° C.), Zr(NMe₂)₄ was dissolved in heptane and was added to aslurry of the respective treated solid oxide in heptane. Zr(NMe₂)₄ wasused at a weight percentage of about 1%, based on the weight of thetreated solid oxide. This mixture was stirred for about 2 to 3 minutes.The solvent was removed under vacuum at a temperature of about 25 to 30°C., resulting in a free-flowing solid, zirconium-containingactivator-support. No subsequent calcining was conducted on thesezirconium-containing activator-supports.

Following the general polymerization procedure provided above, 0.2 mg ofthe metallocene and 200 mg of the activator-support were used forExamples 11-16, and the polymerization process was conducted at areactor temperature of 95° C., a reactor pressure of 420 psig, and areaction time of 60 minutes.

FIG. 4 compares the molecular weight distributions of the polymers ofExamples 11 and 12. As shown in Table III and FIG. 4, polymer producedusing the sulfated alumina activator-support containing zirconium had abroader molecular weight distribution (e.g., higher Mw/Mn and Mz/Mw)than the polymer produced using sulfated alumina Higher molecular weightpolymer was also produced due to the presence of zirconium in theactivator-support, as reflected in the Mw and Mz values in Table III andthe high molecular weight tail illustrated graphically in FIG. 4. Theweight percent of the total polymer of Example 11 having a molecularweight greater than 1,000,000 g/mol was 4.5%, and greater than 3,000,000g/mol was 0.8%.

As compared to the polymers of Examples 13-14, the polymer of Example11, produced using a zirconium-impregnated sulfated alumina activatorsupport, had a higher ratio of Mz/Mw. Surprisingly, the catalystactivity of the zirconium-containing sulfated alumina was far superiorto that of either zirconium-containing chlorided zinc aluminate orfluorided silica-alumina, each evaluated under the same polymerizationconditions and using the same metallocene compound. The catalystactivity of the zirconium-containing sulfated alumina (Example 11) was12 times that of the zirconium-containing fluorided silica-alumina(Example 14) and 40 times that of zirconium-containing chlorided zincaluminate (Example 13).

Examples 15-16 were conducted under the same polymerization conditionsas Examples 11-14, except that a metallocene compound was not used.Rather, 2 mg of Zr(NMe₂)₄ were used to conduct the polymerization. InExample 16, 2 mg of Zr(NMe₂)₄ were impregnated on the sulfated alumina,in the manner described above, to form a zirconium-containingactivator-support. The same amount of Zr(NMe₂)₄ was used in Example 15,except the zirconium was not impregnated onto the sulfated alumina

As compared to the polymer of Example 15, the polymer of Example 16,produced using a zirconium-impregnated sulfated alumina activatorsupport, had a much higher molecular weight, as reflected in both the Mwand the Mz. The weight percent of the total polymer of Example 16 havinga molecular weight greater than 1,000,000 g/mol was about 50%, andgreater than 3,000,000 g/mol was about 20%. Also, unexpectedly, thecatalyst activity of the zirconium-containing sulfated alumina was farsuperior to that of the sulfated alumina without incorporation ofzirconium, each evaluated under the same polymerization conditions andusing the same amount of Zr(NMe₂)₄. The catalyst activity of thezirconium-containing sulfated alumina (Example 16) was over 3 times thatof sulfated alumina without incorporation of zirconium (Example 15).

TABLE III Polymerization Conditions and Polymer Properties of Examples11-16. H₂/Ethylene Activator- g PE Example Type Feed (ppm) Supportproduced 11 Inventive 200 SA-Zr 281 12 Comparative 200 SA 231 13Comparative 200 CZA-Zr   7 14 Comparative 200 FSA-Zr  23 15 Comparative200 SA   4 16 Inventive 200 SA-Zr  13 Mn/1000 Mw/1000 Mz/1000 Mw/ Mz/Example (g/mol) (g/mol) (g/mol) Mn Mw 11  99  370 1116  3.7 3.0 12 132 309  504  2.4 1.6 13  59  981 2673 16.7 2.7 14 260  613 1609  2.4 2.615  47 1168 2903 24.7 2.5 16 270 1814 4238  6.7 2.3

Constructive Example 17 Constructive Synthesis of a Metal-ContainingSulfated Activator-Support in the Vapor Phase

The starting material for Constructive Example 17 can be a sulfatedalumina activator-support prepared in a manner similar to the proceduredescribed above. For instance, approximately 10 g of the sulfatedalumina activator-support are placed in a quartz tube fitted with asintered quartz disk at the bottom. The quartz tube can be, for example,about 1.5 to about 2 inches in diameter. To fluidize the sulfatedalumina, dry air (nitrogen can be substituted) is blown upward throughthe disk at a linear rate of about 0.05 ft/s at 25° C. Volumetric flowrates of about 1.6 to about 1.8 standard cubic feet per hour can beused. An electric furnace around the quartz tube is then turned on andthe temperature is increased to about 600° C. over an approximate90-minute time period. This temperature is maintained for about threehours and then the tube is removed from the furnace and allowed to coolto about 25° C.

Titanium can be impregnated onto the sulfated alumina as follows. About0.1 g of liquid TiCl₄ is injected into the air stream at about 25° C.onto a second porous disk, which is below the sintered quartz disk inthe quartz tube. Air continues to flow upward through both disks,fluidizing the powdered sulfated alumina After about 15 min, it isexpected that all of the TiCl₄ has evaporated and contacted the sulfatedalumina, resulting in a good distribution of, and an almost completeadsorption of, the titanium onto the sulfated alumina. This product is atitanium-containing sulfated alumina activator-support.

The titanium-containing sulfated alumina can be used in combination withan alkyl aluminum co-catalyst to polymerize olefins, such as ethylene,in the absence of a metallocene compound, in a manner similar to Example16. A polymer having a Mw of from about 1,000,000 to about 3,000,000 canbe produced.

The titanium-containing sulfated alumina can be used with a metallocenecompound and an alkyl aluminum co-catalyst to polymerize olefins, suchas ethylene, in a manner similar to Examples 2, 4, and 8. A polymerproduced in this manner will have a molecular weight distribution whichcan be considered to consist of two components, one being a typicalunimodal, bell-shaped curve, and the other being a high molecular weighttail, the high molecular weight tail resulting from thetitanium-containing sulfated alumina.

We claim:
 1. A catalyst composition comprising: a contact product of ametallocene compound and a metal-containing sulfated activator-support,wherein the metal-containing sulfated activator-support is produced by aprocess comprising: (a) contacting a solid oxide with a sulfate compoundto produce a sulfated solid oxide; (b) calcining the sulfated solidoxide to produce a calcined sulfated solid oxide; and (c) contacting thecalcined sulfated solid oxide with: (i) a transition metal compound anda hydrocarbon solvent; or (ii) a vapor comprising a transition metalcompound; to produce the metal-containing sulfated activator-support;wherein the metal-containing sulfated activator-support is not calcined.2. The catalyst composition of claim 1, wherein the catalyst compositionfurther comprises an organoaluminum compound.
 3. The catalystcomposition of claim 2, wherein the catalyst composition has a catalystactivity of greater than about 1000 grams of olefin polymer per gram ofthe metal-containing sulfated activator-support per hour under slurrypolymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and a reactor pressure of 400psig.
 4. The catalyst composition of claim 1, wherein: a weight percentof the transition metal compound to the metal-containing sulfatedactivator-support is in a range from about 0.01 to about 10 percent; andthe transition metal compound comprises titanium, zirconium, hafnium,vanadium, or any combination thereof.
 5. The catalyst composition ofclaim 4, wherein: the catalyst composition further comprises anorganoaluminum compound; the solid oxide is calcined prior to step (a);a ratio of the sulfate compound to the solid oxide is in a range fromabout 1.5 mmol/g to about 10 mmol/g; and the solid oxide comprisessilica, alumina, silica-alumina, or any combination thereof.
 6. Apolymerization process, the polymerization process comprising contactingthe catalyst composition of claim 1 with an olefin monomer andoptionally an olefin comonomer under polymerization conditions toproduce an olefin polymer.
 7. The polymerization process of claim 6,wherein: the catalyst composition is contacted with ethylene and anolefin comonomer comprising 1-butene, 1-hexene, 1-octene, or acombination thereof; and the catalyst composition further comprises anorganoaluminum compound.
 8. The polymerization process of claim 6,wherein: a weight percent of the transition metal compound to themetal-containing sulfated activator-support is in a range from about0.01 to about 10 percent; the transition metal compound comprisestitanium, zirconium, hafnium, vanadium, or any combination thereof; aratio of the sulfate compound to the solid oxide is in a range fromabout 1.5 mmol/g to about 10 mmol/g; and the solid oxide comprisessilica, alumina, silica-alumina, or any combination thereof.
 9. Thepolymerization process of claim 8, wherein: the catalyst composition iscontacted with ethylene and an olefin comonomer comprising 1-butene,1-hexene, 1-octene, or a combination thereof; and the catalystcomposition further comprises an organoaluminum compound.
 10. Thepolymerization process of claim 9, wherein the olefin polymer has az-average molecular weight (Mz) from about 1,000,000 to about 5,000,000g/mol.
 11. A catalyst composition comprising: a contact product of ametallocene compound and a metal-containing sulfated activator-support,wherein the metal-containing sulfated activator-support is produced by aprocess comprising: (a) contacting a solid oxide with a sulfate compoundwhile calcining to produce a calcined sulfated solid oxide; and (b)contacting the calcined sulfated solid oxide with: (i) a transitionmetal compound and a hydrocarbon solvent; or (ii) a vapor comprising atransition metal compound; to produce the metal-containing sulfatedactivator-support; wherein the metal-containing sulfatedactivator-support is not calcined.
 12. The catalyst composition of claim11, wherein the catalyst composition further comprises an organoaluminumcompound.
 13. The catalyst composition of claim 12, wherein the catalystcomposition has a catalyst activity of greater than about 1000 grams ofolefin polymer per gram of the metal-containing sulfatedactivator-support per hour under slurry polymerization conditions, usingisobutane as a diluent, with a polymerization temperature of 90° C., anda reactor pressure of 400 psig.
 14. The catalyst composition of claim11, wherein: a weight percent of the transition metal compound to themetal-containing sulfated activator-support is in a range from about0.01 to about 10 percent; and the transition metal compound comprisestitanium, zirconium, hafnium, vanadium, or any combination thereof. 15.The catalyst composition of claim 14, wherein: the catalyst compositionfurther comprises an organoaluminum compound; the solid oxide iscalcined prior to step (a); a ratio of the sulfate compound to the solidoxide is in a range from about 1.5 mmol/g to about 10 mmol/g; and thesolid oxide comprises silica, alumina, silica-alumina, or anycombination thereof.
 16. A polymerization process, the polymerizationprocess comprising contacting the catalyst composition of claim 11 withan olefin monomer and optionally an olefin comonomer underpolymerization conditions to produce an olefin polymer.
 17. Thepolymerization process of claim 16, wherein: the catalyst composition iscontacted with ethylene and an olefin comonomer comprising 1-butene,1-hexene, 1-octene, or a combination thereof; and the catalystcomposition further comprises an organoaluminum compound.
 18. Thepolymerization process of claim 16, wherein: a weight percent of thetransition metal compound to the metal-containing sulfatedactivator-support is in a range from about 0.01 to about 10 percent; thetransition metal compound comprises titanium, zirconium, hafnium,vanadium, or any combination thereof; a ratio of the sulfate compound tothe solid oxide is in a range from about 1.5 mmol/g to about 10 mmol/g;and the solid oxide comprises silica, alumina, silica-alumina, or anycombination thereof.
 19. The polymerization process of claim 18,wherein: the catalyst composition is contacted with ethylene and anolefin comonomer comprising 1-butene, 1-hexene, 1-octene, or acombination thereof; and the catalyst composition further comprises anorganoaluminum compound.
 20. The polymerization process of claim 19,wherein the olefin polymer has a z-average molecular weight (Mz) fromabout 1,000,000 to about 5,000,000 g/mol.